Organic semiconductor device and method for manufacturing electrode for source / drain thereof

Abstract

The present disclosure provides a fine electrode that can be used for the manufacture of integrated circuits for practical use of organic semiconductor devices without easily changing over time. The present disclosure relates to a source / drain electrode, which is a source / drain electrode of an organic semiconductor device, the source / drain electrode comprising 10 or more groups of electrodes, a channel length between the electrodes of each group being 200 μm or less, and the electrodes of each group having a surface with a surface roughness Rq of 2 nm or less.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to an electrode for source / drain of an organic semiconductor device, an organic semiconductor device using the electrode for source / drain, and a manufacturing method thereof. BACKGROUND

[0002] In recent years, attention to organic semiconductors has been increasing. As a feature of organic semiconductors, unlike conventional inorganic semiconductors such as amorphous silicon and polycrystal silicon, excellent flexibility, inexpensive large-area formation using a roll to roll process, and the like can be cited, and the application of organic semiconductors as post silicon semiconductors to next-generation electronic devices has been studied.

[0003] In a layered device such as an organic field effect transistor (OFET), the following steps are performed: an electrode such as Au is formed on an organic semiconductor layer by vacuum evaporation, and the formed electrode is patterned by a photolithography method. However, it is known that the device characteristics can be deteriorated due to heat damage to the organic semiconductor layer at the time of evaporation of the electrode, or damage to the organic semiconductor layer caused by a resist, an etching solution, or the like at the time of the photolithography process.

[0004] As a method of forming an electrode on an organic semiconductor layer without causing damage to the organic semiconductor layer, a method of forming an electrode pattern on an elastic body having adhesiveness and adhering the elastic body on which the electrode pattern is formed to the organic semiconductor layer is known, and can be used for basic physical property evaluation (Non-Patent Literature 1).

[0005] PRIOR ART DOCUMENTS

[0006] NON-PATENT LITERATURE

[0007] Non-Patent Literature 1: J. A. Rogers et al., Proc. Natl. Acad. Sci. USA 99, 10252 (2002) SUMMARY

[0008] PROBLEMS TO BE SOLVED BY THE INVENTION

[0009] However, in the method of Non-Patent Literature 1, it is difficult to form a fine electrode on an elastic body that easily shrinks, and the organic semiconductor is easily damaged in a short period of time as time passes, and it is difficult to be used for the manufacture of integrated circuits for practical use. Although the reason why the organic semiconductor is damaged in a short period of time as time passes is not clear, it is considered that there are the following reasons: the elastic body that easily shrinks due to temperature or the like and easily changes over time is adhered directly above the organic semiconductor film; or low-molecular siloxane contained in polydimethylsiloxane (PDMS) as the elastic body.

[0010] SOLUTION TO THE PROBLEM

[0011] (1) An electrode for source / drain of an organic semiconductor device,

[0012] The electrode for source / drain includes 10 or more groups of electrodes,

[0013] The channel length between the electrodes of each group is 200 μm or less,

[0014] The electrodes of each group have a surface with a surface roughness Rq of 2 nm or less.

[0015] (2) The electrode for source / drain according to the above (1), wherein,

[0016] The parallelism of the channel length between the electrodes of each group is 1 degree or less.

[0017] (3) The electrode for source / drain according to the above (1) or (2), wherein,

[0018] Further has a protective film composed of an insulating polymer having a glass transition point of 80°C or more and a thickness of 1 μm or less, which is attached to a surface opposite to the surface of the electrodes of each group by electrostatic force and extends along at least a part of the channel of each group.

[0019] (4) The electrode for source / drain according to any one of the above (1) to (3), wherein,

[0020] The electrode has a plating layer.

[0021] (5) An organic semiconductor device including a gate electrode, a gate insulating film, an organic semiconductor film, and the electrode for source / drain according to any one of the above (1) to (4).

[0022] (6) The organic semiconductor device according to the above (5), wherein,

[0023] The surface roughness Rq of the surface of the organic semiconductor film, which is in contact with the electrodes of each group, is 2 nm or less.

[0024] (7) A method for manufacturing an electrode for source / drain of an organic semiconductor device, wherein,

[0025] The method for manufacturing an electrode for source / drain of an organic semiconductor device includes the steps of:

[0026] Preparing a substrate having a surface roughness Rq of 2 nm or less;

[0027] Forming a release layer on the surface of the substrate;

[0028] forming 10 or more groups of electrodes for source and drain with a channel length of 200 μm or less on the peeling layer;

[0029] forming a protective film on the peeling layer and the electrodes;

[0030] forming a processing film on the protective film;

[0031] peeling the interface of the peeling layer and the electrodes and the protective film to obtain an electrode film including the electrodes, the protective film, and the processing film; and

[0032] removing the processing film.

[0033] (8) The method for manufacturing an electrode for source and drain of an organic semiconductor device according to the above (7), wherein

[0034] the step of forming a peeling layer includes the steps of:

[0035] UV ozone treating the surface of the substrate to form a hydroxyl group on the surface of the substrate; and

[0036] SAM treating the surface of the substrate on which the hydroxyl group is formed.

[0037] (9) The method for manufacturing an electrode for source and drain of an organic semiconductor device according to the above (7), wherein

[0038] the step of forming a peeling layer includes the steps of:

[0039] forming a lyophobic polymer layer on the surface of the substrate;

[0040] arranging a photomask or a metal mask on the substrate on which the lyophobic polymer layer is formed;

[0041] UV irradiating the substrate from the side on which the photomask or the metal mask is arranged to decompose the lyophobic polymer layer at the irradiated site, and forming a hydroxyl group at the site where the lyophobic polymer layer is decomposed; and

[0042] SAM treating the site on which the hydroxyl group is formed,

[0043] the step of forming 10 or more groups of electrodes for source and drain with a channel length of 200 μm or less includes:

[0044] applying a conductive ink containing metal particles on the peeling layer; and

[0045] The substrate on which the release layer to which the conductive ink is applied is formed is subjected to non-electrolytic plating using the metal particles as a catalyst to form 10 or more electrodes having a plating layer for source / drain electrodes with a channel length of 200 μm or less.

[0046] (10) A method for manufacturing an organic semiconductor device, wherein

[0047] The method for manufacturing an organic semiconductor device includes the steps of:

[0048] A substrate having a surface roughness Rq of 2 nm or less is prepared;

[0049] A release layer is formed on the surface of the substrate;

[0050] An electrode for source / drain electrodes with a channel length of 200 μm or less is formed on the release layer;

[0051] A protective film is formed on the release layer and the electrode;

[0052] A processing film is formed on the protective film;

[0053] The interface between the release layer and the electrode and the protective film is released to obtain an electrode film including the electrode, the protective film, and the processing film;

[0054] The electrode film is disposed on an organic semiconductor film; and

[0055] The processing film is removed.

[0056] (11) The method for manufacturing an organic semiconductor device according to the above (10), wherein

[0057] The step of forming a release layer includes the steps of:

[0058] The surface of the substrate is subjected to UV ozone treatment to form a hydroxyl group on the surface of the substrate; and

[0059] The surface of the substrate on which the hydroxyl group is formed is subjected to SAM treatment.

[0060] (12) The method for manufacturing an organic semiconductor device according to the above (10), wherein

[0061] The step of forming a release layer includes the steps of:

[0062] A lyophobic polymer layer is formed on the surface of the substrate;

[0063] A photomask or a metal mask is disposed on the substrate on which the lyophobic polymer layer is formed;

[0064] UV irradiation is performed on the substrate from the side on which the photomask or the metal mask is arranged, the lyophobic polymer layer of the irradiated portion is decomposed, and a hydroxyl group is formed at the portion where the lyophobic polymer layer is decomposed; and

[0065] The portion where the hydroxyl group is formed is subjected to SAM treatment,

[0066] The step of forming 10 or more groups of electrodes for source / drain electrodes having a channel length of 200 μm or less includes:

[0067] A conductive ink liquid containing metal particles is applied to the peeling layer; and

[0068] The substrate on which the peeling layer to which the conductive ink liquid is applied is subjected to non-electrolytic plating using the metal particles as a catalyst, and 10 or more groups of electrodes for source / drain electrodes having a channel length of 200 μm or less are formed with plating layers.

[0069] Effects of the Invention

[0070] According to the present disclosure, a fine electrode can be provided, which can be used for the manufacture of integrated circuits for actual use of organic semiconductor devices without easily changing over time. BRIEF DESCRIPTION OF DRAWINGS

[0071] Figure 1 is a microscope photograph obtained by observing the source / drain electrode of the present disclosure from the surface.

[0072] Figure 2 is a cross-sectional schematic view of the source / drain electrode of the present disclosure.

[0073] Figure 3 is a cross-sectional schematic view of the source / drain electrode of the present disclosure with a protective film.

[0074] Figure 4 is a cross-sectional schematic view of the source / drain electrode of the present disclosure with a protective film.

[0075] Figure 5 is a cross-sectional schematic view of an organic semiconductor device including a gate electrode, a gate insulating film, an organic semiconductor film, and the source / drain electrode of the present disclosure.

[0076] Figure 6 is a cross-sectional schematic view of an organic semiconductor device including a gate electrode, a gate insulating film, an organic semiconductor film, and the source / drain electrode of the present disclosure.

[0077] Figure 7 is a cross-sectional schematic view of a substrate on which a peeling layer is formed.

[0078] Figure 8is a cross-sectional view of a substrate on which an electrode is formed on a peeling layer.

[0079] Figure 9 is a cross-sectional view of a substrate on which a protective film, a peeling layer, and an electrode are formed.

[0080] Figure 10 is a cross-sectional view of a substrate on which a processing film, a peeling layer, an electrode, and a protective film are formed.

[0081] Figure 11 is a cross-sectional view of an electrode film in which a protective film is sandwiched by an electrode and a processing film.

[0082] Figure 12 is a cross-sectional view of an electrode film disposed on an organic semiconductor film 66.

[0083] Figure 13 is a photograph of an electrode film in which a PMMA film as a protective film is sandwiched by an Au electrode and a PVA film of a water-soluble polymer.

[0084] Figure 14 is a microscope photograph in which an Au electrode pattern of Figure 13 is enlarged.

[0085] Figure 15 is a photograph of an obtained organic semiconductor device.

[0086] Figure 16 is a laser confocal microscope photograph of a monomolecular layer film of C9-DNBDT-NW formed by a continuous edge casting method.

[0087] Figure 17 is a result of measurement of a monomolecular layer film of C9-DNBDT-NW of Figure 16 by an atomic force microscope (AFM).

[0088] Figure 18 is a graph showing transfer characteristics of a relationship between a gate voltage and a drain current in a saturation region.

[0089] Figure 19 is a graph showing transfer characteristics of a relationship between a gate voltage and a drain current in a linear region.

[0090] Figure 20 is a graph showing output characteristics of a relationship between a drain voltage and a drain current based on a gate voltage.

[0091] Figure 21 is a graph showing transfer characteristics of a relationship between a gate voltage and a drain current in a saturation region.

[0092] Figure 22 is a graph showing transfer characteristics of a relationship between a gate voltage and a drain current in a linear region.

[0093] Figure 23 is a graph showing an output characteristic of a drain voltage based on a gate voltage and a drain current.

[0094] Figure 24 is a graph showing a transfer characteristic of a gate voltage and a drain current in a saturation region.

[0095] Figure 25 is a graph showing a transfer characteristic of a gate voltage and a drain current in a linear region.

[0096] Figure 26 is a graph showing an output characteristic of a drain voltage based on a gate voltage and a drain current.

[0097] Figure 27 is a graph showing a transfer characteristic of a gate voltage and a drain current in a saturation region.

[0098] Figure 28 is a graph showing a transfer characteristic of a gate voltage and a drain current in a linear region.

[0099] Figure 29 is a graph showing an output characteristic of a drain voltage based on a gate voltage and a drain current.

[0100] Figure 32 is a top view photograph of one example of the electrode for source / drain of the present disclosure.

[0101] Figure 33 is an enlarged photograph of a group of electrodes for source / drain surrounded by a broken line of Figure 34

[0102] is a graph showing a transfer characteristic of a gate voltage and a drain current in a saturation region. Figure 35

[0103] is a graph showing a transfer characteristic of a gate voltage and a drain current in a linear region. Figure 36

[0104] is a graph showing an output characteristic of a drain voltage based on a gate voltage and a drain current. Figure 37

[0105] is a graph showing a transfer characteristic of a gate voltage and a drain current in a saturation region. Figure 38

[0106] is a graph showing a transfer characteristic of a gate voltage and a drain current in a linear region. Figure 39

[0107] Figure 40 ​This is a graph showing the output characteristics based on the relationship between the drain voltage and drain current, which is determined by the gate voltage.

[0108] Figure 41 It is a graph showing the transfer characteristics of the relationship between the gate voltage and the drain current in the saturation region.

[0109] Figure 42 It is a graph showing the transfer characteristics of the relationship between the gate voltage and the drain current in a linear region.

[0110] Figure 43 This is a graph showing the output characteristics based on the relationship between the drain voltage and drain current, which is determined by the gate voltage.

[0111] Figure 44 This is an example of the AFM measurement results for an electrode with a surface roughness Rq of 0.6 nm.

[0112] Figure 45 It is a cross-sectional schematic diagram of an organic semiconductor device including a gate electrode, a gate insulating film, an organic semiconductor film, and source / drain electrodes of this disclosure.

[0113] Figure 46 It is a cross-sectional schematic diagram of an organic semiconductor device including a gate electrode, a gate insulating film, an organic semiconductor film, and source / drain electrodes of this disclosure.

[0114] Figure 47 This means that for each V G -V th Channel length L and R total A diagram showing the relationship between / W.

[0115] Figure 48 It represents V G -V th With R C A diagram showing the relationship between / W.

[0116] Figure 49 This is a schematic cross-sectional view of a substrate with a hydrophobic polymer layer.

[0117] Figure 52 This is a cross-sectional schematic diagram showing the shape of a substrate with a hydrophobic polymer layer being irradiated with vacuum ultraviolet light from the side where a photomask or metal mask is provided.

[0118] Figure 53 This is a schematic cross-sectional view of a substrate with hydroxyl groups formed at the site where the hydrophobic polymer layer has been decomposed.

[0119] Figure 50 This is a schematic cross-sectional view of the surface of a substrate in which a self-assembled monolayer is formed at the site where hydroxyl groups are formed.

[0120] Figure 51is a cross-sectional schematic view showing a configuration of an electrode formed by applying a conductive ink by a doctor blade method and patterning on a substrate on which a self-assembled monolayer is formed.

[0121] Figure 54 is a photograph showing an appearance of a patterned coating film composed of Ag particles formed by a coating method.

[0122] Figure 55 is a photograph showing evaluation of wettability of CYTOP (registered trademark) and octane before irradiation of vacuum ultraviolet light.

[0123] Figure 56 is a photograph showing evaluation of wettability of CYTOP (registered trademark) and octane after formation of a self-assembled monolayer.

[0124] Figure 57 is a cross-sectional schematic view of a substrate on which an electrode having a plated layer is formed.

[0125] Figure 58 is a photograph showing an appearance of a source / drain electrode having an Au plated layer.

[0126] Figure 59 is a cross-sectional schematic view of a bottom gate / top contact structure of an organic field effect transistor.

[0127] Figure 60 is a cross-sectional schematic view of an electrode film including an electrode having an Au plated layer, a Parylene (registered trademark) protective film, and a PVA-treated film.

[0128] Figure 61 is a graph showing a measurement result of a work function with respect to photon energy (hv) of the electrode. 1 / 2

[0129] Figure 62 is a photograph showing an appearance of a source / drain electrode having a channel length / channel width of 100 μm / 315 μm.

[0130] Figure 63 is a graph showing transfer characteristics of a relationship between a gate voltage and a drain current in a saturation region.

[0131] Figure 64 is a graph showing transfer characteristics of a relationship between a gate voltage and a drain current in a linear region.

[0132] Figure 65 is a graph showing output characteristics of a relationship between a drain voltage and a drain current based on a gate voltage.

[0133] Figure 66 is a photograph showing an appearance in which a range for evaluation of contact resistance is shown by a broken line.​

[0134] Figure 1 This means that for each V G -V th Channel length L and R total A diagram showing the relationship between / W.

[0135] Figure 1 It represents V G -V th With R C A diagram showing the relationship between / W.

[0136] Figure 1 It is a photograph of the appearance of a patterned coating film composed of Ag particles formed by a coating method. Detailed Implementation

[0137] This disclosure pertains to electrodes, which are source / drain electrodes for organic semiconductor devices, comprising 10 or more groups of electrodes, wherein the channel length between each group of electrodes is less than 200 μm, and each group of electrodes has a surface roughness Rq of less than 2 nm.

[0138] Figure 1 The image shows an example of the source / drain electrodes of this disclosure, namely a photograph of the upper surface of 50 sets of electrodes. Figure 2 The middle shows Figure 2 A magnified photograph of a group of source / drain electrodes surrounded by dashed lines. Figure 1 The image shows three sets of magnified microscopic photographs of an example of the source / drain electrodes of this disclosure. Figure 30 The diagram shows a cross-sectional schematic of one set of source / drain electrodes of this disclosure. Figure 41 yes Figure 41 A schematic diagram of the cross section of A-A.

[0139] exist Figure 1 In this structure, 50 groups of source / drain electrodes are formed in a 1.5 cm square area. The channel length of each group of electrodes is 200 μm, the surface roughness Rq of each group of electrodes is less than 2 nm, and the channel width of each group of electrodes is 1000 μm. Figure 2 An example of AFM measurement results for the source / drain electrodes of this disclosure is shown. Figure 3 The results are AFM measurements of an Au electrode with a surface roughness Rq of 0.6 nm, which is equipped with a PMMA protective film and a PVA treatment film.

[0140] The source / drain electrode disclosed herein comprises 10 or more sets of source / drain electrodes, preferably 50 or more sets, more preferably 1,000 or more sets, even more preferably 10,000 or more sets, and even more preferably 50,000 or more sets.

[0141] In Figure 4 the channel length L of the first group of electrodes 10, 20 is 10 μm and the channel width W is 500 μm. The channel length L of the second group of electrodes 12, 22 is 20 μm and the channel width W is 500 μm. The channel length L of the third group of electrodes 14, 24 is 40 μm and the channel width W is 500 μm.

[0142] The channel length between the electrodes of each group of electrodes for source / drain of the present disclosure is 200 μm or less, preferably 100 μm or less, more preferably 10 μm or less, further preferably 1 μm or less, and still further preferably 0.5 μm or less. In the present application, the channel length refers to the channel length within each group of electrodes (one element). In 10 or more electrodes, the channel length can be different from each other as long as it is 200 μm or less. The lower limit of the channel length is not particularly limited, and it is preferably about 0.05 μm, which is the same order as the lower limit of the thickness of the protective film described below. The channel length of the electrodes for source / drain of the present disclosure is small, and thus the organic semiconductor device including the electrodes for source / drain of the present disclosure can operate at a high frequency in practical use. The frequency in practical use is preferably 10 kHz or more, more preferably 100 kHz or more, further preferably 1 MHz or more, and still further preferably 10 MHz or more. The channel length is an average value of values obtained by measuring three points in the channel width direction within each group of electrodes (one element). The measurement positions of the three points are positions of the center point and two points on both sides of the center point, which are equally divided into four.

[0143] The channel width is not particularly limited, and for example, it can be 100 μm to 10,000 μm.

[0144] The electrodes for source / drain of the present disclosure have a surface having a surface roughness Rq of 2 nm or less. In Figure 3 In the present embodiment, the surface 101 of the electrode 10 and the surface 201 of the electrode 20 have a surface roughness Rq of 2 nm or less. The surface roughness Rq of the electrode is preferably 1 nm or less, and more preferably 0.5 nm or less. The lower limit of the surface roughness Rq of the electrode is not particularly limited, and for example, it can be 0.1 nm.

[0145] The electrodes for source / drain of the present disclosure have a surface having a surface roughness Rq of 2 nm or less. In

[0146] The surface roughness Rq of the surface of the organic semiconductor film in contact with the electrode is also small, and is preferably 2 nm or less. If the organic semiconductor film and the electrode are arranged in such a manner that the surface roughness of each is small, the adhesion between the organic semiconductor film and the electrode can be improved, and the structure of the organic semiconductor film can not be damaged. Therefore, the organic semiconductor device including the electrode for source / drain electrode of the present disclosure can exhibit good characteristics. The surface roughness Rq of the organic semiconductor film is preferably 1 nm or less, and more preferably 0.5 nm or less. The lower limit of the surface roughness Rq of the organic semiconductor film is not particularly limited, and can be, for example, 0.1 nm. The surface roughness Rq of the electrode is the root mean square roughness of the values obtained by measuring three points using an atomic force microscope (AFM) on the surface of each group (one element) of the electrode in contact with the organic semiconductor film after peeling from the peeling layer, and is the square root of the values obtained by averaging the squares of the deviations from the measurement curve. The measurement positions of the three points are the positions of the center point and two points on both sides of the center point by dividing the longest line on the surface of the electrode into four. The longest line on the surface of the electrode is, for example, the diameter in the case of a circular electrode, and the diagonal line in the case of a quadrangular electrode.

[0147] For the electrode for source / drain electrode of the present disclosure, the parallelism of the channel length between the electrodes of each group is preferably 1 degree or less, more preferably 0.5 degrees or less, further preferably 0.1 degrees or less, and more further preferably 0.01 degrees or less. The parallelism of the channel length refers to the angle formed by the edges of the electrodes of each group (one element) of the electrode facing each other to form the channel length. The parallelism of the channel length of each group of electrodes is excellent, and therefore the organic semiconductor device including the electrode for source / drain electrode of the present disclosure can exhibit characteristics as designed.

[0148] The method for measuring the angle (parallelism) formed by the edges of the opposing electrodes is as follows: SEM observation of the channel length is performed at the largest possible magnification within the entire range including the channel length and the channel width of each group (one element) of the electrode. Based on the SEM image obtained by the SEM observation, the positions of the edges of five points including both end portions of the channel width are measured by dividing the channel width into four in the channel width direction for the edges (both edges) of the opposing electrodes of each group (one element) of the electrode, and a straight line is determined by the least squares method such that the sum of the squares of the distances from the five measured points becomes the smallest. The angle formed by the two determined straight lines is measured, and the parallelism is calculated.

[0149] The material of the electrode is not particularly limited as long as it is a material that can be used for an organic semiconductor device, and is preferably Au, Ag, carbon, a conductive polymer, or a combination thereof, and more preferably Au.

[0150] The thickness of the electrode is preferably 20-200 nm, more preferably 25-100 nm, and even more preferably 30-50 nm.

[0151] The source / drain electrodes of this disclosure preferably further have a protective film, which is made of an insulating polymer having a thickness of less than 1 μm and a glass transition point of 80°C or higher, and is attached to the surfaces of electrodes 10 and 20 opposite to surfaces 101 and 201 by electrostatic force, and extends along at least a portion of the channel.

[0152] The protective film is made of a non-adhesive insulating polymer with a glass transition point of 80°C or higher, thus it will not cause long-term damage to the organic semiconductor film, and the organic semiconductor is not easily affected by time. Furthermore, by setting it to a thin film with a thickness of 1 μm or less, adhesion caused by electrostatic forces can be achieved between the protective film and the electrode, and between the protective film and the organic semiconductor film. In this application, the time-dependent changes of the organic semiconductor are evaluated by measuring the mobility of the semiconductor device containing the organic semiconductor over a specified period, preferably 4 weeks or more, more preferably 8 weeks or more.

[0153] Although theoretically unrestricted, it can be considered that, as mentioned above, if a viscous elastomer with a low glass transition point is used, the organic semiconductor film is easily damaged in a short period of time. However, an insulating polymer with a thickness of less than 1 μm and a glass transition point of more than 80°C is bonded to the organic semiconductor film by electrostatic force. Therefore, the organic semiconductor film has high long-term stability and is not easily changed over time.

[0154] Figure 5 The diagram shows a cross-sectional schematic of the source / drain electrodes 10 and 20 of this disclosure, each equipped with a protective film 30. The thickness of the protective film 30 is preferably 1 μm or less, more preferably less than 1 μm, and even more preferably 0.5 μm or less. The lower limit of the protective film thickness is not particularly limited, but from the viewpoint of stably forming an insulating film, it is 0.05 μm.

[0155] The glass transition point of the protective film 30 is 80°C or higher, preferably 90°C or higher, and more preferably 100°C or higher. The glass transition point of the insulating polymer having a glass transition point within this range is sufficiently higher than room temperature; therefore, when configured to contact the organic semiconductor film, it is less likely to cause degradation of the organic semiconductor film, and the organic semiconductor is less prone to change over time.

[0156] The protective film 30 is attached to the surfaces of electrodes 10 and 20 opposite to surfaces 101 and 201 by electrostatic force. For example... Figure 6 As shown, the protective film 30 only needs to extend along at least a portion of the channel 40 in the region indicated by the dashed line between electrodes 10 and 20. Preferably, the protective film 30 is as follows: Figure 5extends along substantially the entire region of the trench 40.

[0157] The protective film 30 has substantially no adhesion and is attached to the electrodes 10, 20 by electrostatic force. The protective film 30 makes the handling of the electrodes after the formation of the electrodes easy, can prevent the electrodes from being damaged at the time of removal of the processing film to be described later, and can suppress the peeling of the electrodes from the organic semiconductor film in the organic semiconductor device using the electrodes of the present disclosure.

[0158] The material of the protective film 30 is preferably polymethyl methacrylate (PMMA) having a glass transition point of about 100°C, a fluorine-based polymer such as CYTOP (registered trademark) having a glass transition point of about 108°C, parylene (registered trademark) having a glass transition point of about 109°C, or polyadamantyl methacrylate (PADMA) having a glass transition point of 200°C or higher.

[0159] The electrode for source / drain of the present disclosure preferably has a plating layer. By the electrode for source / drain having a plating layer, the work function of the electrode can be controlled, and the injection of carriers from the electrode into the organic semiconductor can be improved.

[0160] The plating layer is preferably an Au plating layer, an Ag plating layer, a Pt plating layer, or a Cu plating layer, and more preferably an Au plating layer. By the electrode for source / drain having the preferred metal plating layer, an electrode having a high work function that is advantageous for the injection of carriers into the organic semiconductor can be formed.

[0161] The work function is measured by photoelectron yield spectroscopy (PYS) using the following formula:

[0162] Y ∝ (hv - W) 1 / 2 ∝ hv - W F

[0163] (In the formula, Y is the photoelectron yield, h is Planck's constant, v is the vibration number of a photon, and W F is the work function). When light having an energy of a certain value or more is irradiated to a substance, an electron is released from the substance by the photoelectric effect. The energy at which the electron starts to be released corresponds to the work function. For PYS, the released electron is measured while changing the energy of the irradiated light, and the measurement is performed. In the measurement, the photoelectron yield (Y) indicating the proportion of the number of released electrons to the number of irradiated photons is set, the energy of the irradiated light is set as h v, and the work function of the measured substance is set as W F .

[0164] Y ∝ (hv - W) F n

[0165] ​n is a value determined depending on the kind of the material, and in the case of a metal, n = 2. Y 1 / 2 is plotted against h v, the regions before and after the site of W F are linearly approximated, respectively. W F

[0166] Figure 6 and Figure 5 are cross-sectional schematic diagrams of the organic semiconductor devices 100, 200 including the gate electrode 54, the gate insulating film 52, the organic semiconductor film 66, and the source / drain electrodes 10, 20 of the present disclosure. Figure 6 is a cross-sectional schematic diagram of a top gate / top contact structure, Figure 7 is a cross-sectional schematic diagram of a bottom gate / top contact structure.

[0167] In the organic semiconductor devices 100, 200 of Figure 8 and Figure 9 , the electrodes 10, 20 are included in the form of source / drain electrodes.

[0168] The gate electrode 54 can be composed of a material of a gate electrode used in the past, and for example, can be doped-Si. The doped-Si can be a material used in the past, which is sufficiently low in electric resistance value as a gate electrode.

[0169] The gate insulating film 52 can also be composed of a material of a gate insulating film used in the past.

[0170] In the top gate / top contact structure, the gate insulating film 52 can also be composed integrally with the protective film 30 composed of an insulating polymer.

[0171] The base layer 56 can also be a layer including a substrate used in the past, a smoothing layer, and a layer subjected to surface modification. The base layer 56 can be exemplified by, for example, a layer in which a glass, a surface of the glass is coated with a film of parylene (registered trademark), trimethoxy (2-phenylethyl) silane (β-PTS), or the like; a layer in which a plastic substrate of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or the like, a surface of the plastic substrate of PET, PEN, or the like is coated with a film of parylene (registered trademark) or the like; a layer in which a device such as a transistor is fabricated on these substrates; or a layer in which an interlayer insulating film of parylene (registered trademark), aluminum oxide, or the like is deposited on these devices.

[0172] ​In the case of preparing the electrode for source / drain of the present disclosure with the protective film 30, the protective film 30 can be directly used as the insulating film in the organic semiconductor device 100, 200, or the protective film 30 can be temporarily dissolved and the protective film 30 can be reformed, or the protective film 30 can be reformed as one with the gate insulating film 52.

[0173] In the organic semiconductor device, it is preferable that the surface roughness Rq of the surface of the organic semiconductor film which is in contact with the electrode be 2 nm or less. When the organic semiconductor film and the electrode are arranged in a manner that the surface roughness of each is small, the adhesion between the organic semiconductor film and the electrode can be improved, and the contact resistance can be reduced. The surface roughness Rq of the organic semiconductor film is the root mean square roughness of the values obtained by measuring three points on the surface of the organic semiconductor film using an atomic force microscope (AFM), and is the square root of the values obtained by averaging the squares of the deviations from the measurement curve. The measurement positions of the three points are positions of the center point and two points on both sides of the center point, which divide the longest line in the plane of the organic semiconductor film into four. The longest line in the plane of the organic semiconductor film refers to, for example, the diameter in the case of a circular organic semiconductor film, and the diagonal line in the case of a quadrangular organic semiconductor film.

[0174] The contact resistance R C W is preferably 200 Ω·cm or less, more preferably 175 Ω·cm or less, further preferably 150 Ω·cm or less, and still further preferably 125 Ω·cm or less. C R is the contact resistance, and W is the channel width.

[0175] The contact resistance of the organic semiconductor device is evaluated using the Transmission Line Method (TLM). The TLM is based on the following equation, and the resistance R total W is indirectly estimated from the y-intercept of the regression line. C W is indirectly estimated from the y-intercept of the regression line. total W can be obtained by dividing the drain voltage V D by the drain current I D，lin .

[0176]

[0177] (In the equation, R total is the resistance of the organic semiconductor device, R C is the contact resistance, L is the channel length, μ int is the mobility of the organic semiconductor device as it is, excluding the influence of the contact resistance, and W is the channel width.i V for the capacitance per unit area G V for the gate voltage th V for the threshold voltage.

[0178] The organic semiconductor device including the electrode for source / drain according to the present disclosure can be an organic EL (electroluminescence) element, an organic solar cell element, an organic photoelectric conversion element, an organic transistor element, an organic field effect transistor (OFET) element, or the like.

[0179] The present disclosure also relates to a method for manufacturing an electrode for source / drain of an organic semiconductor device, the method including the steps of: preparing a substrate having a surface roughness Rq of 2 nm or less; forming a release layer on the surface of the substrate; forming 10 or more groups of electrodes for source / drain having a channel length of 200 μm or less on the release layer; forming a protective film on the release layer and the electrodes; forming a processing film on the protective film; releasing the interface between the release layer and the electrodes and the protective film to obtain an electrode film including the electrodes, the protective film, and the processing film; and removing the processing film.

[0180] According to the method of the present disclosure, an electrode for source / drain of an organic semiconductor device including 10 or more groups of electrodes, each group of electrodes having a channel length of 200 μm or less between the electrodes of the group, and each group of electrodes having a surface with a surface roughness Rq of 2 nm or less can be obtained.

[0181] In the method of the present disclosure, a substrate having a surface roughness Rq of 2 nm or less is prepared. The surface roughness Rq of the substrate is preferably 1 nm or less, more preferably 0.5 nm or less. The lower limit of the surface roughness Rq of the substrate is not particularly limited, and can be, for example, 0.1 nm. According to the method of the present disclosure, an electrode for source / drain having substantially the same surface roughness as the surface roughness Rq of the substrate can be obtained. The surface roughness Rq of the substrate is the root mean square roughness of the values obtained by measuring 3 points on the surface of the substrate using an atomic force microscope (AFM), and is the square root of the values obtained by averaging the squares of the deviations from the measurement curve. The measurement positions of the 3 points are the positions of the center point and the 2 points on both sides of the center point, which are quartered by the longest line in the plane of the substrate. The longest line in the plane of the substrate refers to, for example, the diameter in the case of a circular substrate, or the diagonal line in the case of a quadrangular substrate.

[0182] The substrate having the above-described surface roughness Rq is preferably a glass substrate or a silicon substrate, and is, for example, EAGLE XG (registered trademark) of Corning Inc. The substrate having the above-described surface roughness Rq can also be prepared by polishing a substrate such as a glass substrate or a silicon substrate.

[0183] In the method disclosed herein, a release layer is formed on the surface of the prepared substrate.

[0184] One preferred embodiment of forming the release layer includes: treating the surface of the prepared substrate with UV ozone (UV / O3) to form hydroxyl groups on the surface of the substrate; and treating the surface of the substrate with the hydroxyl groups with SAM (Self-Assembled Monolayer) treatment.

[0185] By performing UV ozone treatment, organic matter on the surface of the substrate can be oxidized and removed, generating hydroxyl groups on the surface of the oxide film. For example, UV ozone treatment can involve atmospheric oxygen (O2) absorbing ultraviolet light at a wavelength of approximately 185 nm to generate ozone (O3). The generated ozone (O3) then absorbs ultraviolet light at a wavelength of approximately 254 nm to generate O2 and reactive oxygen species. These reactive oxygen species oxidize and decompose the organic matter on the substrate surface, generating hydroxyl groups on the surface of the oxide film.

[0186] By performing SAM treatment on the surface of a substrate with hydroxyl groups, a release layer can be formed on the surface of the substrate. Figure 10 The diagram shows a cross-sectional schematic of a substrate 60 with a release layer 62 formed by UV ozone treatment and SAM treatment. The SAM treatment is performed to adjust the surface energy.

[0187] Release layer 62 is a film used to peel the electrode and protective film formed in subsequent processes from the substrate 60. Release layer 62 remains on the substrate 60 side, allowing the electrode and protective film to peel off. Release layer 62 is preferably a self-assembled monolayer. The adhesion between the electrode and the self-assembled monolayer is weaker than the adhesion between the electrode and the protective film, and the adhesion between the protective film and the self-assembled monolayer is weaker than the adhesion between the protective film and the processed film.

[0188] The self-assembled monolayer preferably has a straight-chain alkyl or fluoroalkyl group, with terminal groups being alkyl, fluoroalkyl, phenyl, or fluorophenyl. Such a self-assembled monolayer is a hydrophobic membrane with a contact angle preferably of 80 degrees or more, more preferably 90 degrees or more, and even more preferably 95 degrees or more, thus allowing for easy peeling off of electrodes and protective films formed on the self-assembled monolayer in subsequent processes.

[0189] In straight-chain alkyl (CH) n In this context, n is not particularly limited, but is preferably 8 to 18. Similarly, in straight-chain fluoroalkyl (CF) compounds... n In this context, n is not specifically limited, but is preferably 1 to 10.

[0190] Self-assembled monolayers are, for example, decyltrimethoxysilane (DTS), triethoxy-1H, 1H, 2H, 2H-heptadecafluorodecylsilane (F-SAM), or trimethoxy(2-phenylethyl)silane (β-PTS). DTS has a contact angle of about 101 degrees, F-SAM has a contact angle of about 110 degrees, and β-PTS has a contact angle of about 80 degrees, and thus is easily peeled off from the substrate more easily than the electrode and the protective film formed on the self-assembled monolayer in a subsequent process.

[0191] The SAM treatment can be performed by a gas phase method or a liquid phase method.

[0192] The gas phase method is a method of exposing a substrate on which a hydroxyl group is formed to a saturated vapor of a SAM molecule. By this, the SAM molecule is dehydrated and condensed with the hydroxyl group, and a self-assembled monolayer can be formed on the surface of the substrate.

[0193] Exposing the substrate to the saturated vapor of the SAM molecule can be performed, for example, by disposing a SAM solution and the substrate in a closed container, forming a saturated vapor atmosphere of the SAM molecule by heating, and standing the substrate in the saturated vapor atmosphere of the SAM molecule. The standing time can be about 2 to 5 hours. The heating temperature can be about 120 to 150°C.

[0194] After the substrate is exposed to the saturated vapor of the SAM molecule, the substrate is cleaned. In the case of DTS, the substrate is cleaned with toluene and then with 2-propanol. In the case of F-SAM, the substrate is cleaned with 2-propanol. In the case of β-PTS, the substrate is cleaned with toluene and then with 2-propanol.

[0195] The liquid phase method is a method of immersing a substrate on which a hydroxyl group is formed on the surface in a solution in which a SAM molecule is dissolved. By this, a self-assembled monolayer can also be formed on the surface of the substrate.

[0196] In the method of the present disclosure, an electrode is formed on a peeling layer formed on a substrate. Figure 10 A cross-sectional schematic view of a substrate 60 on which an electrode 10, 20 is formed on a peeling layer 62 is shown in FIG. 6.

[0197] As a method of forming the electrode, there is no particular limitation, and a film of an electrode material or an electrode can be formed using a vacuum process or a solution process.

[0198] For example, a printing method such as gravure printing, screen printing, inkjet printing, or the like can be used to form the electrode on the peeling layer. Alternatively, a film of an electrode material can be applied to the peeling layer by vacuum evaporation or spin coating, dip coating, roll coating, spray coating, flow coating, blade coating, push coating, or the like, and the formed film of the electrode material can be patterned using a photolithography method to form the electrode.

[0199] The method of forming the electrode is selected in accordance with the electrode material. In the case of Au as the electrode material, vacuum evaporation is preferably performed, and the electrode is formed by patterning using photolithography.

[0200] In the case of Ag as the electrode material, a printing method such as gravure printing, screen printing, inkjet printing, and the like is preferably used to form the electrode on the release layer.

[0201] In the case of carbon as the electrode material, a method such as spraying, blade coating, and the like is preferably used to form the electrode on the release layer.

[0202] In the case of a conductive polymer as the electrode material, a method such as spin coating, push coating, and the like is preferably used to form the electrode on the release layer.

[0203] Another embodiment of forming the release layer preferably includes the steps of forming a lyophilic polymer layer on the surface of the substrate, disposing a photomask or a metal mask on the substrate on which the lyophilic polymer layer is formed, performing UV (ultraviolet) irradiation on the substrate from the side on which the photomask or the metal mask is disposed, decomposing the lyophilic polymer layer at the irradiated site, forming a hydroxyl group at the site where the lyophilic polymer layer is decomposed, and performing SAM treatment on the site where the hydroxyl group is formed.

[0204] In the present embodiment including the steps of forming a lyophilic polymer layer, forming a hydroxyl group at the site where the lyophilic polymer layer is decomposed, and performing SAM treatment on the site where the hydroxyl group is formed, forming 10 or more groups of electrodes having a channel length of 200 μm or less includes the steps of applying a conductive ink containing metal particles on the release layer, and performing non-electrolytic plating on the substrate on which the release layer to which the conductive ink is applied is formed using the metal particles as a catalyst to form 10 or more groups of electrodes having a channel length of 200 μm or less for the source and the drain provided with a plated layer.

[0205] In the present embodiment including the steps of forming a lyophilic polymer layer, forming a hydroxyl group at the site where the lyophilic polymer layer is decomposed, and performing SAM treatment on the site where the hydroxyl group is formed, patterning of the electrode is performed using the difference in wettability of the lyophilic polymer layer and the site on which SAM treatment is performed with respect to the conductive ink.

[0206] Forming the lyophilic polymer layer on the surface of the substrate can be performed by a coating method. As the coating method, a method conventionally used can be used, and for example, an edge cast method, a continuous edge cast method, a drop cast method, a spin coating method, a printing method (inkjet method, gravure printing method), a dispenser method, and a method such as spraying, dip coating, die coating, roll coating, bar coating, blade coating, and the like can be used.

[0207] The thickness of the lyophobic polymer layer is preferably 1 to 50 nm, more preferably 2 to 30 nm, further preferably 3 to 20 nm, and still further preferably 5 to 15 nm. By having the lyophobic polymer layer with the above-mentioned preferable thickness, the surface roughness of the electrode to be formed can be reduced.

[0208] The material of the lyophobic polymer layer is preferably a fluorine-based polymer such as CYTOP (registered trademark), polytrifluoroethylene (PTFE), perfluoroalkoxy alkane (PFA), or the like. The surface of the substrate can be subjected to UV treatment before the lyophobic polymer layer is formed on the surface of the substrate.

[0209] The photomask or the metal mask disposed on the substrate on which the lyophobic polymer layer is formed is not particularly limited as long as it is a member capable of shielding UV light, and for example, it can be chromium.

[0210] The UV light is irradiated from the side on which the photomask or the metal mask is disposed, with respect to the substrate on which the lyophobic polymer layer is formed, so that the lyophobic polymer layer at the irradiation site is decomposed, and a hydroxyl group is formed at the site where the lyophobic polymer layer is decomposed. The surface is hydrophilized by the formation of the hydroxyl group.

[0211] The lyophobic polymer layer is decomposed by the UV irradiation, and a part of the lyophobic polymer layer can remain without being decomposed. The hydroxyl group can be formed on the substrate exposed by the decomposition of the lyophobic polymer layer, on the remaining lyophobic polymer layer, or on both the exposed substrate and the remaining lyophobic polymer layer.

[0212] The UV light is preferably vacuum ultraviolet light. By irradiating vacuum ultraviolet light, the lyophobic polymer layer can be more efficiently decomposed to form a hydroxyl group at the site where the lyophobic polymer layer is decomposed. The center wavelength of the vacuum ultraviolet light is about 10 to 200 nm.

[0213] The site where the hydroxyl group is generated by the UV irradiation is subjected to SAM treatment. The SAM treatment is performed on the entire substrate where the hydroxyl group is generated by the UV irradiation, but a self-assembled monolayer can be selectively formed only at the UV irradiation site.

[0214] The self-assembled monolayer preferably has a straight-chain alkyl group or a straight-chain fluoroalkyl group, and the terminal group is an alkyl group, a fluoroalkyl group, a phenyl group, or a fluorophenyl group. Such a self-assembled monolayer makes it easy to peel off the electrode formed on the self-assembled monolayer by coating and plating in a subsequent process.

[0215] Among the straight-chain alkyl groups (CH2)n n n is not particularly limited and is preferably 8 to 18. Similarly, among the straight-chain fluoroalkyl groups (CF2)n n n is not particularly limited and is preferably 1 to 10.

[0216] The self-assembled monolayer is, for example, decyltrimethoxysilane (DTS), triethoxy-lH, lH, 2H, 2H-heptadecafluorodecylsilane (F-SAM), or trimethoxy(2-phenylethyl)silane (β-PTS), and is preferably F-SAM. It is easy to peel off the electrode formed on the self-assembled monolayer by coating and plating in the subsequent process.

[0217] The conductive ink containing metal particles is coated on the peeling layer. The method of coating the conductive ink is not particularly limited, and can be, for example, a blade coating method or the like. The conductive ink can be selectively coated only on the portion on which the SAM treatment is performed. With respect to the solvent of the conductive ink, the portion on which the SAM treatment is performed is lyophilic, and the photo mask or the metal mask portion (lyophobic polymer layer) is lyophobic, and thus the conductive ink can be substantially selectively coated only on the portion on which the SAM treatment is performed. According to this method, from the viewpoint of forming the parallelism of the channel length with high precision to be 0.1 degrees or less, the lower limit value of the channel length is preferably about 8 μm, and high-precision patterning of L / S = 10 μm / 10 μm, for example, can be performed.

[0218] The metal particles of the conductive ink are preferably Ag, Au, Pt, Cu, Pd, Ni, or a combination thereof.

[0219] The solvent of the conductive ink is a solvent in which the lyophobic polymer layer is relatively lyophobic and the portion on which the SAM treatment is performed is relatively lyophilic. The solvent of the conductive ink is preferably a solvent in which the difference between the contact angle with the lyophobic polymer layer and the contact angle with the portion on which the SAM treatment is performed is preferably 3 degrees or less, and more preferably 5 degrees or more. The solvent of the conductive ink is further preferably an organic solvent of octane, toluene, tetradecane, butyl acetate, or a combination thereof. The solid content concentration in the solvent of the conductive ink is preferably 0.1 to 30 wt%.

[0220] The electrode having the plating layer is formed by non-electrolytic plating using the metal particles of the applied conductive ink as a catalyst. By using the plating layer to form the source / drain electrode, the work function of the electrode can be controlled, and the injection of carriers from the electrode into the organic semiconductor can be improved. Furthermore, by non-electrolytic plating using the metal particles of the applied conductive ink as a catalyst, a source / drain electrode having a surface roughness Rq of 2 nm or less and a plating layer formed between the island-shaped metal particles can be obtained. That is, in the present embodiment including the formation of a lyophobic polymer layer, the formation of a hydroxyl group at a site where the lyophobic polymer layer is decomposed, and the SAM treatment of the site where the hydroxyl group is formed, the source / drain electrode includes the metal particles and the plating layer. The plating layer is preferably an Au plating layer, an Ag plating layer, a Pt plating layer, or a Cu plating layer, and more preferably an Au plating layer. By providing the source / drain electrode with an Au plating layer, an electrode having a high work function that is advantageous for the injection of carriers into the organic semiconductor can be formed.

[0221] The non-electrolytic plating can be a conventional autocatalytic reduction plating. The plating solution contains, in addition to metal ions and a reducing agent, a buffering material for preventing changes in pH, a complexing agent for stabilizing the metal ions, and the like. When a substrate coated with a conductive ink containing metal particles is immersed in this plating solution, metal ions in the plating solution are deposited by a reduction reaction using the metal particles as a catalyst, and a plating film can be formed.

[0222] In the method of the present disclosure, the electrode can be formed by the above process, and thus 10 or more groups of fine electrodes having a channel length of 200 μm or less and a surface roughness Rq of 2 nm or less can be provided. Such electrodes can be used in the manufacture of integrated circuits for practical use of organic semiconductor devices. Furthermore, as described above, after the electrode is formed on the release layer, the electrode can be peeled from the release layer and disposed on the organic semiconductor film as described below, and thus the organic semiconductor film is less likely to be damaged and less likely to change over time. In the method of the present disclosure, the electrode can also be formed by the above process, and thus electrodes having a parallelism of 1 degree or less in the channel length in each group of a plurality of groups of 10 or more groups can be obtained.

[0223] In the method of the present disclosure, a protective film is formed on the release layer and the electrode. Figure 10 A cross-sectional schematic view of a substrate 60, a release layer 62, and electrodes 10 and 20 formed with a protective film 30 is shown in FIG. 12.

[0224] The protective film 30 can inhibit peeling, damage, and the like of the electrode when a processing film is removed in a subsequent process. The protective film can also inhibit the peeling of the electrode from the organic semiconductor film in an organic semiconductor device using the electrode produced by the method of the present disclosure.

[0225] The protective film is made of an insulating polymer with a thickness of less than 1 μm, is electrostatically attached to the side of the electrode opposite to the surface of the electrode, and extends along at least a portion of the channel.

[0226] The protective film 30 can be a fluorinated polymer such as polymethyl methacrylate (PMMA) CYTOP (registered trademark), parylene (perelin (registered trademark)) or polyadamantyl methacrylate (PADMA) that does not affect the properties of the organic semiconductor film.

[0227] The protective film 30 is preferably formed by spin coating or chemical vapor deposition.

[0228] When forming electrodes by vacuum evaporation, the protective film is preferably PMMA, CYTOP (registered trademark), or PADMA formed by spin coating. Spin coating is simple to use in practice and is therefore preferred. The spin coating speed, time, and other conditions can be the same as those previously used, as long as they are appropriately set according to the material of the protective film.

[0229] When electrodes are formed by coating or by a combination of coating and plating, the protective film is preferably made of parylene (Pyrelin (registered trademark)) which can be formed by chemical vapor deposition (CVD) as a dry process. The protective film of Pyrelin (registered trademark) further prevents the dissolution of electrodes formed by coating. CVD can be performed using conventional methods, for example, heating the dimer to 170°C to vaporize it, and further heating it to 690°C to cause the dimer to crack and generate monomers. Then, a substrate is placed, and the generated monomers are allowed to flow into a chamber maintained at room temperature and rapidly cooled. The monomers are then polymerized on the substrate surface through free radical polymerization to form a polymeric state, thus forming a film.

[0230] In the method disclosed herein, a processing film is formed on the formed protective film. Figure 11 The diagram shows a cross-sectional view of a substrate 60 with a processing film 64, a release layer 62, electrodes 10 and 20, and a protective film 30.

[0231] like Figure 13 As shown, the processing film 64 is formed for peeling electrodes 10, 20 and protective film 30 from the release layer 62. In subsequent processes, if the electrode film, protective film and processing film are disposed on the organic semiconductor film without removing the processing film 64, the processing film 64 can also function as a processing film for disposing of the electrode film with the protective film on the organic semiconductor film.

[0232] The thickness of the processing film 64 is not particularly limited as long as it is a thickness capable of processing the electrodes 10, 20 and the protective film 30, and is preferably 10 μm or more. The upper limit of the thickness of the processing film 64 is not particularly limited, but the greater the thickness, the more time-consuming the removal of the processing film, and thus it is preferably 100 μm or less.

[0233] The processing film 64 is preferably made of a material corresponding to the protective film 30. In the case where the protective film 30 is made of a water-insoluble polymer, the processing film 64 is preferably a water-soluble polymer film. In the case where the protective film 30 is made of a polymer that is not dissolved in an organic solvent, the processing film 64 is preferably an organic solvent-soluble polymer film. By making the processing film 64 the above-mentioned preferred polymer film, only the processing film 64 is dissolved without dissolving the protective film 30 in a solution process, and thus the processing film can be easily removed.

[0234] In the case where the processing film 64 is a water-soluble polymer film, a water solution of a water-soluble polymer is applied to the protective film to form the water-soluble polymer film. The water-soluble polymer film can be dissolved in water and removed after the electrodes 10, 20 and the protective film 30 are peeled from the peeling layer 62. In the case where the electrodes film, the protective film and the processing film are arranged on the organic semiconductor film without removing the processing film 64 in the subsequent process, the water-soluble polymer film can be dissolved in water and removed after the electrodes and the protective film are arranged on the organic semiconductor film.

[0235] The water-soluble polymer of the water-soluble polymer film is preferably polyvinyl alcohol (PVA), polyacrylic acid, dextran or polymethacrylic acid, and more preferably polyvinyl alcohol (PVA).

[0236] In the case where the processing film 64 is an organic solvent-soluble polymer film, a water solution of an organic solvent-soluble polymer is applied to the protective film to form the organic solvent-soluble polymer film. The organic solvent-soluble polymer film can be dissolved in an organic solvent and removed after the electrodes 10, 20 and the protective film 30 are peeled from the peeling layer 62. In the case where the electrodes film, the protective film and the processing film are arranged on the organic semiconductor film without removing the processing film 64 in the subsequent process, the organic solvent-soluble polymer film can be dissolved in an organic solvent and removed after the electrodes and the protective film are arranged on the organic semiconductor film.

[0237] The organic solvent-soluble polymer of the organic solvent-soluble polymer film is preferably polymethyl methacrylate (PMMA), polystyrene (PS), polyacrylonitrile (PAN) or polyethylene (PE), and more preferably polymethyl methacrylate (PMMA).

[0238] After the processing film is formed on the protective film, the interface between the peeling layer and the electrodes and the protective film is peeled, and an electrode film including the electrodes, the protective film and the processing film is obtained.

[0239] By adhering a tape such as a Kapton tape to the surface of the processing film and stretching, as shown in Figure 14 the interface between the peeling layer 62 and the electrodes 10, 20 and the protective film 30 is peeled, and an electrode film 600 including the electrodes 10, 20, the protective film 30 and the processing film 64 is obtained. Figure 13 A cross-sectional schematic view of the electrode film 600 with the electrodes 10, 20 and the processing film 64 sandwiching the protective film 30 is shown in

[0240] Figure 14 A photograph of the appearance of the electrode film with a PMMA film as the protective film sandwiched by Au electrodes and a PVA film of a water-soluble polymer is shown in Figure 12 A microscope photograph of the Au electrode pattern of Figure 12 is shown in Figure 15 The first to third groups of electrodes from the top have a channel width of 500 μm, and each has a channel length of 10 μm, 20 μm and 40 μm.

[0241] The processing film 64 is removed from the electrode film 600. The removal of the processing film 64 can be performed by a method corresponding to the material constituting the processing film.

[0242] In the case where the processing film is constituted by a water-soluble polymer, water is used to remove the processing film from the electrode film.

[0243] In the case where water is used to remove the processing film, it is preferable to first drop water on the processing film, and after the processing film is substantially peeled, water is added until the entire electrode film is immersed in water, and the processing film is stirred until it is substantially completely removed from the electrode film by being dissolved.

[0244] By removing the processing film, an electrode provided with a protective film can be obtained. In the case where the protective film is constituted by a water-insoluble polymer, it can also be removed by an organic solvent such as acetonitrile. In the case where the protective film is constituted by a polymer that is insoluble in an organic solvent, it can also be removed by a solvent such as a fluorine-based solvent. As long as a solvent that dissolves the polymer constituting the protective film is used, it is possible.

[0245] The present disclosure also relates to a method for manufacturing an organic semiconductor device, the method including: preparing a substrate having a surface roughness Rq of 2 nm or less; forming a separation layer on a surface of the substrate; forming 10 or more source / drain electrodes each having a channel length of 200 μm or less on the separation layer; forming a protective film on the separation layer and the electrodes; forming a processing film on the protective film; separating the separation layer from the electrodes and the protective film to obtain an electrode film including the electrodes, the protective film, and the processing film; disposing the electrode film on an organic semiconductor film; and removing the processing film.

[0246] As shown in FIG. 6, the electrode film 600 obtained in the method for manufacturing the source / drain electrodes of the organic semiconductor device is disposed on the organic semiconductor film 66. When the electrode film 600 is disposed on the organic semiconductor film 66, the electrode film is brought into contact with the organic semiconductor film in such a manner that the protective film 30 is tightly bonded to the organic semiconductor film 66. Figure 15

[0247] Figure 13 FIG. 7 is a cross-sectional view of an example of the organic semiconductor device 200 having the electrode film 600 including the electrodes 10, 20, the protective film 30, and the processing film 64 disposed on the organic semiconductor film 66. After the electrode film 600 is disposed on the organic semiconductor film 66, the processing film 64 is removed.

[0248] The organic semiconductor device 200 is a bottom-gate / top-contact organic field effect transistor. The organic semiconductor film 66 is formed on the gate electrode 74 and the base layers (gate insulating films) 70, 72. The gate electrode 74 can be a material used in the past, such as doped Si or the like. The base layers 70, 72 can also be a material used in the past, such as SiO2, Parylene (registered trademark), or the like.

[0249] When the electrode film 600 is disposed on the organic semiconductor film 66, it is preferable to heat the temperature of the organic semiconductor film 66 to 50 to 90°C, and more preferably to 60 to 80°C. The heating can be performed using a hot plate or the like.

[0250] By heating the organic semiconductor film 66 to the preferable temperature, the protective film 30 and the processing film 64 become soft, and the protective film 30 can be easily disposed in such a manner that the protective film 30 follows the surface shape of the electrodes 10, 20 and adheres to the surface of the organic semiconductor film 66, and the tightness of the protective film 30 to the organic semiconductor film 66 is improved. When the organic semiconductor film 66 is heated to the preferable temperature, the entire substrate on which the organic semiconductor film 66 is disposed can be heated.

[0251] ​Preferably, the organic semiconductor film 66 is heated from the substrate side after the electrode film 600 is disposed on the organic semiconductor film 66 at room temperature. By heating the organic semiconductor film 66 after the electrode film 600 is disposed on it, the protective film 30 can be more effectively attached to the surface of the organic semiconductor film 66 in a manner that follows the surface shape of the electrodes 10 and 20, thereby further improving the adhesion between the protective film 30 and the organic semiconductor film 66.

[0252] After the electrode film is disposed on the organic semiconductor film, the processing film 64 is removed. The removal of the processing film 64 can be performed by a method appropriate to the material constituting the processing film.

[0253] When the processing membrane is made of a water-soluble polymer, it is preferable to apply water to the electrode film disposed on the organic semiconductor membrane while the substrate, the organic semiconductor membrane, and the electrode film are heated to remove the processing membrane.

[0254] When using water to remove the treatment membrane, the temperature of the membrane can be lowered to 20–40°C. Preferred methods for applying water to the electrode membrane include first adding water droplets to the treatment membrane, then adding water after the treatment membrane has substantially peeled off until the entire electrode membrane is submerged, and stirring until the treatment membrane dissolves and is substantially completely removed from the electrode membrane.

[0255] By removing the processing film, an organic semiconductor device with electrodes and a protective film disposed on the organic semiconductor film can be obtained. Figure 14 The image shows the appearance of the resulting organic semiconductor device. Figure 13 In the organic semiconductor device shown, an Au electrode and a PMMA protective film are formed on the organic semiconductor film.

[0256] According to the method disclosed herein, organic field-effect transistors and other organic semiconductor devices can be fabricated without damaging the organic semiconductor layer.

[0257] The organic semiconductor film is preferably an organic semiconductor single crystal film.

[0258] The average thickness of the organic semiconductor single crystal film is 2–100 nm, preferably 4–20 nm. Good device characteristics can be obtained by keeping the average thickness of the organic semiconductor single crystal film within this range. The average thickness of the organic semiconductor single crystal film can be measured using a stylus surface shape analyzer or an atomic force microscope.

[0259] The organic semiconductor single-crystal film preferably has a thickness of 1 molecular layer (monomolecular layer) to 50 molecular layers, more preferably 1 molecular layer to 10 molecular layers, further preferably 1 molecular layer to 5 molecular layers, and still further preferably 1 molecular layer to 3 molecular layers in the thickness direction. The organic semiconductor single-crystal film most preferably has a thickness of 1 molecular layer, but can have a thickness of 2 molecular layers or more in the thickness direction. The number of molecular layers of the organic semiconductor single-crystal film can be measured by atomic force microscopy.

[0260] The smaller the number of molecular layers of the organic semiconductor, the lower the resistance of the bulk region of the organic semiconductor, and the lower the contact resistance. The contact resistance is the sum of the resistance of the bulk region of the organic semiconductor when transporting charges from the electrode / organic semiconductor interface to the channel region, and the resistance when injecting charges from the electrode to the organic semiconductor layer. The reason for this is that the channel region, in which carriers are accumulated, corresponds to one to several molecular layers of the organic semiconductor layer at the interface of the gate insulating film, and the layers other than this hinder the smooth injection of carriers from the electrode to the channel.

[0261] In the method of the present disclosure, the electrode formed on the flat substrate is disposed on the organic semiconductor film, and thus does not apply heat damage imparted in the vapor deposition process or damage caused by the resist, etching solution, or the like during the photolithography process, and even if the organic semiconductor film is an organic semiconductor single-crystal film having a thickness of 1 molecular layer in the thickness direction, the organic semiconductor film does not become damaged and functions as an organic semiconductor device.

[0262] The thickness of the 1 molecular layer of the organic semiconductor single-crystal film is preferably 2 to 6 nm, and more preferably 2 to 4 nm. The thickness of the 1 molecular layer of the organic semiconductor single-crystal film can be measured by combining single-crystal X-ray structure analysis and atomic force microscope observation.

[0263] The area of the organic semiconductor single-crystal film is preferably 2 mm 2 More preferably, the area is 10 mm 2 Further preferably, the area is 100 mm 2 Still further preferably, the area is 1000 mm 2 Still further preferably, the area is 10000 mm 2 The upper limit of the area of the organic semiconductor single-crystal film is not particularly limited and is limited by the size of the manufacturing equipment, and can be set to 10 m 2 In the past, the largest area of the organic semiconductor single-crystal film that could be obtained using the vapor phase growth method was about 1 mm 2 Therefore, the organic semiconductor device of the present disclosure can have a large area as described above.

[0264] The organic semiconductor single-crystal film includes a single domain or multiple domains, and preferably includes a single domain. The domains of the organic semiconductor single-crystal film can be determined by single-crystal X-ray diffraction. The organic semiconductor single-crystal film preferably has a thickness of 0.005 mm 2 More preferably, 0.5 mm 2 Further preferably, 2.0 mm 2 The single domain has a continuous area of 0.5 mm

[0265] The organic semiconductor single-crystal film preferably exhibits a mobility of 0.5 cm 2 More preferably, 3.0 cm 2 Further preferably, 5.0 cm 2 Still more preferably, 7.5 cm 2 Yet more preferably, 10 cm 2 The organic semiconductor single-crystal film preferably exhibits a mobility of 0.5 cm

[0266] The type of the organic semiconductor constituting the organic semiconductor film is not particularly limited, and for example, a polycyclic aromatic compound having 4 or more rings, or a polycyclic compound formed from one or more unsaturated five-membered heterocyclic compounds and a plurality of benzene rings can be used.

[0267] Further, the organic semiconductor constituting the organic semiconductor film is preferably a material having a high self-condensation function, and for example, a p-type organic semiconductor Cn-DNBDT-NW represented by the following formula (1) exhibiting a high mobility can be listed.

[0268]

[0269] In formula (1), n can be 1 to 14. The self-condensation function refers to a tendency that the molecules spontaneously condense when precipitating from a solvent, and easily crystallize.

[0270] Other examples of the organic semiconductor constituting the organic semiconductor film are shown in the following formula (2) to formula (6).

[0271]

[0272] In the polythiophene semiconductor represented by formula (2), R 1 and R 2 are each independently a hydrogen atom or an alkyl group having 4 to 10 carbon atoms. The alkyl group can include a heteroatom (typically selected from an oxygen atom and a sulfur atom). Further, R 1 and R 2 may form a ring together. For the reason of the self-condensation ability, R 1 and R2 Each is independently an alkyl group having 5 to 8 carbon atoms or hydrogen atoms. More preferably, it is R. 1 and R 2 Each can be independently a hydrogen atom or a hexyl group.

[0273] n represents an integer from 5 to 100. n represents the average number of thiophene monomer units in the polythiophene semiconductor, i.e., the length of the polythiophene chain. From the viewpoint of forming a single crystal film, n is preferably 50 or less.

[0274]

[0275] In equation (3), R 3 R 4 R 5 and R 6 Each is independently a hydrogen atom or an alkyl group having 1 to 14 carbon atoms. The alkyl group may contain heteroatoms (typically selected from oxygen and sulfur atoms), and the hydrogen atoms in the alkyl group may optionally be substituted with substituents such as halogen atoms. For self-aggregation reasons, R is preferred. 4 =R 5 R is preferred. 3 =R 6 From a solubility point of view, R is preferred. 4 and R 5 It is a hydrogen atom and R 3 and R 6 Each is independently an alkyl group having 1 to 14 carbon atoms, or R 3 and R 6 It is a hydrogen atom and R 4 and R 5 Each is independently an alkyl group having 1 to 14 carbon atoms. More preferably, R 3 and R 6 It is a hydrogen atom and R 4 and R 5 Each alkyl group is independently composed of 1 to 14 carbon atoms. For reasons of self-aggregation, the preferred number of carbon atoms for alkyl groups is 4 to 12, and more preferably 6 to 10.

[0276]

[0277] In equation (4), R 7 R 8 R 9 and R 10 Each is independently a hydrogen atom or an alkyl group having 1 to 14 carbon atoms. The alkyl group may contain heteroatoms (typically selected from oxygen and sulfur atoms), and the hydrogen atoms in the alkyl group may optionally be substituted with substituents such as halogen atoms. For self-aggregation reasons, R is preferred. 7 =R 9 R is preferred.8 =R 10 From a solubility point of view, R is preferred. 7 and R 9 It is a hydrogen atom and R 8 and R 10 Each is independently an alkyl group having 1 to 14 carbon atoms, or R 8 and R 10 It is a hydrogen atom and R 7 and R 9 Each is independently an alkyl group having 1 to 14 carbon atoms. More preferably, R 8 and R 10 For hydrogen atoms, R 7 and R 9 Each alkyl group is independently composed of 1 to 14 carbon atoms. For reasons of self-aggregation, the preferred number of carbon atoms for the alkyl group is 6 to 13, and more preferably 8 to 10.

[0278]

[0279] In equation (5), R 11 R 12 R 13 and R 14 Each alkyl group is independently composed of hydrogen atoms or alkyl groups having 1 to 14 carbon atoms. The alkyl group may contain heteroatoms (typically selected from oxygen and sulfur atoms), and the hydrogen atoms in the alkyl group may also be substituted with substituents such as halogen atoms. For self-aggregation reasons, R is preferred. 11 =R 13 R is preferred. 12 =R 14 From a solubility point of view, R is preferred. 11 and R 13 It is a hydrogen atom and R 12 and R 14 Each is independently an alkyl group having 1 to 14 carbon atoms, or R 12 and R 14 It is a hydrogen atom and R 11 and R 13 Each is independently an alkyl group having 1 to 14 carbon atoms. More preferably, R 12 and R 14 It is a hydrogen atom and R 11 and R 13 Each alkyl group is independently composed of 1 to 14 carbon atoms. For reasons of self-aggregation, the preferred number of carbon atoms for the alkyl group is 5 to 12, and more preferably 8 to 10.

[0280]

[0281] In equation (6), R 15 R16 , R 17 , and R 18 are each independently a hydrogen atom or an alkyl group having 1 to 14 carbon atoms. The alkyl group can contain a hetero atom (typically selected from an oxygen atom and a sulfur atom), and the hydrogen atom in the alkyl group can be substituted with a substituent such as a halogen atom. From the viewpoint of self-aggregation ability, R 15 = R 17 , and R 16 = R 18 is preferred. From the viewpoint of solubility, it is preferred that R 16 and R 18 are hydrogen atoms and R 15 and R 17 are each independently an alkyl group having 1 to 14 carbon atoms, or R 15 and R 17 are hydrogen atoms and R 16 and R 18 are each independently an alkyl group having 1 to 14 carbon atoms. More preferably, R 16 and R 18 are hydrogen atoms and R 15 and R 17 are each independently an alkyl group having 1 to 14 carbon atoms. From the viewpoint of self-aggregation ability, the number of carbon atoms in the alkyl group is preferably 5 to 12, more preferably 8 to 10.

[0282] Another other example of the organic semiconductor constituting the organic semiconductor film is shown in the following Formula (7) to Formula (15). In Formula (7) to Formula (15), R can use a linear alkyl group, a branched alkyl group, a fluorinated linear / branched alkyl group, a triisopropylsilyl ethynyl group, a phenyl group, or the like.

[0283]

[0284]

[0285] The organic semiconductor film can be confirmed to be a single crystal by observation with a transmission electron microscope (TEM).

[0286] The organic semiconductor single crystal film can be formed using a coating method. As the coating method, a method used conventionally can be used, and for example, an edge casting method, a continuous edge casting method, a drop casting method, a spin coating method, a printing method (an inkjet method, a gravure printing method), a dispenser method, a spray coating method, a dip coating method, a die coating method, a roll coating method, a bar coating method, a blade coating method, or the like can be used. Among them, the continuous edge casting method can obtain an organic semiconductor single crystal film having a thickness in which the film thickness is controlled to be very thin, and is easy to control to be about 1 to 3 molecular layers, and thus is preferred.

[0287] It is preferable to provide a carrier injection promoting film between the electrode and the organic semiconductor film. By providing the carrier injection promoting film between the electrode and the organic semiconductor film, injection of carriers into the organic semiconductor film can be promoted.

[0288] The carrier injection promoting film can be provided between the electrode and the organic semiconductor film in an island shape.

[0289] The thickness of the carrier injection promoting film is preferably 1 to 4 nm, and more preferably 2 to 3 nm.

[0290] The carrier injection promoting layer is formed on the peeling layer, and an electrode material is vacuum-deposited on the carrier injection promoting layer, and is patterned by photolithography. Subsequently, the member on which the protective film is formed can be peeled, and the carrier injection promoting layer, the electrode, and the protective film can be arranged so that the carrier injection promoting layer is in contact with the organic semiconductor film. After the carrier injection promoting layer is formed on the peeling layer, instead of the vacuum deposition method, a conductive ink can be applied to the carrier injection promoting layer, and then electrolytic plating can be performed to form the electrode.

[0291] The carrier injection promoting layer is preferably 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ).

[0292] The carrier injection promoting layer can be formed on the peeling layer by vacuum deposition.

[0293] The surface of the electrode can be modified by a self-assembled monolayer of pentafluorobenzenethiol (PFBT) or 4-methylbenzenethiol (MBT). Thereby, the work function of the electrode can be controlled, and injection of carriers from the electrode into the organic semiconductor can be improved.

[0294] In the case where the electrode is formed of PFBT or MBT, the electrode film that has been peeled is immersed in ethanol in which PFBT or MBT is dissolved. Thereby, PFBT or MBT can be formed on the surface of the electrode.

[0295] Example

[0296] (Example 1)

[0297] An EAGLE glass (EAGLE XG (registered trademark) of Corning Inc.) was prepared as a substrate, and UV ozone (UV / O3) treatment was performed to form a hydroxyl group on the surface of the glass. The UV ozone treatment was performed by UV irradiation for 15 minutes using a UV lamp UV253H (wavelength 184.9 nm and 253.7 nm) of Filgen Co., Ltd. in an oxygen atmosphere.

[0298] A glass substrate with hydroxyl groups was subjected to SAM treatment, which formed a self-assembled monolayer of decyltrimethoxysilane (DTS) on the surface of the glass substrate as a release layer. The SAM treatment was performed as follows: a DTS solution and the glass substrate with hydroxyl groups were prepared in a sealed container, heated to 120°C to form a saturated vapor atmosphere of DTS molecules, and the glass substrate with hydroxyl groups was left to stand in the saturated vapor atmosphere of DTS molecules for 3 hours. Then, it was cleaned with toluene and then with 2-propanol.

[0299] Au electrodes were patterned on a glass substrate with a self-assembled monolayer of DTS by vacuum evaporation and photolithography to form 16 groups of Au electrodes with a thickness of 40 nm and channel length / channel width of 100 μm / 500 μm, 80 μm / 500 μm, 60 μm / 500 μm, 40 μm / 500 μm, 20 μm / 500 μm and 10 μm / 500 μm, for a total of 96 groups.

[0300] A solution of 3% by mass polymethyl methacrylate (PMMA) dissolved in butyl acetate was spin-coated onto a glass substrate with an Au electrode. For spin-coating, the rotation speed was increased to 500 rpm within 1 second, maintained at 500 rpm for 5 seconds, and then maintained at 2000 rpm for 40 seconds. The spin was then stopped, and the substrate was dried at 80°C for 30 minutes to remove the solvent, resulting in a protective PMMA film with a thickness of 75 nm.

[0301] A 5% by mass aqueous solution of polyvinyl alcohol (PVA) was coated onto a PMMA protective film and dried at 50°C for 2 hours to form a PVA treatment film with a thickness of 10 μm.

[0302] The electrode film, which includes the Au electrode, the PMMA protective film, and the PVA processing film, was peeled off by bonding the processing film with Kapton tape and stretching the Kapton tape. Figure 14 The image shows the appearance of an electrode film with an Au electrode sandwiched between a PVA-treated film and a PMMA protective film. Figure 4 shown in the Figure 2 A magnified microscope image of the Au electrode pattern. Figure 30 The first to third groups of electrodes, starting from the top, have a channel width of 500 μm and channel lengths of 10 μm, 20 μm, and 40 μm, respectively.

[0303] An electrode film comprising an Au electrode, a PMMA protective film, and a PVA treatment film was placed on a glass plate using a weight to fix the Au electrode. Next, water was added dropwise to the PVA treatment film. After the treatment film was essentially peeled off, the temperature was lowered to 30°C, and water was added until the entire electrode film was submerged. The mixture was stirred in the water for 3 hours until the PVA was completely dissolved, at which point the treatment film was removed, thus creating a film as shown in the image.Figure 31 Au electrode with PMMA protective film.

[0304] Next, the Au electrode with the PMMA protective film was immersed in acetonitrile at 30°C for 30 minutes to remove the PMMA protective film, and an Au electrode as shown in Figure 30

[0305] The channel length / channel width of the electrodes of each of the 64 groups of the obtained Au electrodes 64 was 100 μm / 500 μm, 80 μm / 500 μm, 60 μm / 500 μm, 40 μm / 500 μm, 20 μm / 500 μm, and 10 μm / 500 μm, respectively, and the surface roughness Rq of the electrodes was 0.6 nm. The parallelism of the channel length of each group of electrodes (one element) was 0.1 degrees or less.

[0306] (Example 2)

[0307] Au electrodes of 50 groups having a thickness of 40 nm and a channel length / channel width = 200 μm / 1000 μm were formed, and an Au electrode was produced in the same manner as in Example 1, except for this. Figure 12 A photograph of the upper surface on which Au electrodes of 50 groups having a thickness of 40 nm and a channel length / channel width = 200 μm / 1000 μm were formed in a square of 1.5 cm is shown in Figure 42 An enlarged photograph of the source / drain electrode of one group surrounded by the dotted line of Figure 18

[0308] The channel length / channel width of the electrodes of each of the 50 groups of the obtained Au electrodes 50 was 200 μm / 1000 μm, and the surface roughness Rq of the electrodes was 0.6 nm. The parallelism of the channel length of each group of electrodes (one element) was 0.1 degrees or less.

[0309] (Example 3)

[0310] An electrode film including an Au electrode, a PMMA protective film, and a PVA treatment film was obtained by the same method as in Example 1.

[0311] A powder of a p-type organic semiconductor C9-DNBDT-NW of the following formula (16) that shows a high mobility was prepared as an organic semiconductor.

[0312]

[0313] An organic semiconductor solution was prepared by dissolving the organic semiconductor powder in a solvent using 3-chlorothiophene as the solvent.

[0314] ​​Prepare a substrate consisting of a 500 μm thick doped Si gate electrode, a 100 nm thick SiO2 layer, and a 70 nm thick pyrene (diX-SR (registered trademark)).

[0315] An organic semiconductor single-crystal film was fabricated by coating an organic semiconductor solution onto a substrate heated to 80°C using a continuous edge casting method. The surface roughness Rq of the organic semiconductor film was 0.2 nm.

[0316] A laminate of doped Si, SiO2, pyrene (diX-SR (registered trademark)), and an organic semiconductor film is placed on a heating plate and heated to 80°C, while simultaneously... Figure 19 As shown schematically, an electrode thin film is disposed on an organic semiconductor film in such a way that the electrode is in contact with the organic semiconductor film.

[0317] Water was added dropwise to the PVA treatment membrane while it was heated to 80°C. After the treatment membrane was essentially peeled off, the temperature was lowered to 30°C and water was added until the entire electrode film was immersed in water. The mixture was stirred in the water for 3 hours until the PVA was completely dissolved, at which point the treatment membrane was removed, producing a product like... Figure 20 An organic field-effect transistor with a bottom-gate / top-contact structure is shown schematically.

[0318] Among the transistors fabricated with different channel lengths / channel widths, for transistors with channel lengths / channel widths of 100μm / 500μm, in Figure 21 The graph shown illustrates the transfer characteristics of the relationship between the gate voltage and drain current in the saturation region. Figure 22 The graph shown illustrates the transfer characteristics of the relationship between the gate voltage and drain current in a linear region. Figure 23 The graph shows the output characteristics, representing the relationship between drain voltage and drain current based on gate voltage. Mobility in the saturation region is shown at 10 cm⁻¹. 2 / V·s, the migration rate in the linear region is shown at 10cm. 2 / V·s indicates a very high mobility. In the mobility calculation, the capacitance of the insulating film layered with SiO2 and pyrene (registered trademark) is calculated using theoretical values.

[0319] (Example 4)

[0320] For the transistor fabricated in Example 3 with a channel length / channel width of 10μm / 500μm, in Figure 16 The graph shown illustrates the transfer characteristics of the relationship between the gate voltage and drain current in the saturation region. Figure 17 The graph shown illustrates the transfer characteristics of the relationship between the gate voltage and drain current in a linear region. Figure 16The graph shows the output characteristics representing the relationship between drain voltage and drain current based on gate voltage. The mobility in the saturation region is shown to be 3.6 cm⁻¹. 2 / V·s, the mobility in the linear region is shown to be 7.2cm. 2 / V·s, even for short-channel devices with a channel length of 10μm, good mobility can be obtained.

[0321] (Example 5)

[0322] The release layer was changed to triethoxy-1H,1H,2H,2H-heptadecylsilane (F-SAM), and the organic semiconductor device was fabricated in the same manner as in Example 3.

[0323] The mobility of the fabricated transistor with a channel length / channel width of 100 μm / 500 μm was measured, and the results showed the same mobility as in Example 3.

[0324] (Example 6)

[0325] An Au electrode with a channel length / channel width of 200 μm / 1000 μm was formed using the same electrode pattern as in Example 2. Otherwise, an electrode film comprising an Au electrode, a PMMA protective film, and a PVA processing film was obtained using the same method as in Example 1. Furthermore, the release layer was changed to F-SAM, and the phenelzine (diX-SR (registered trademark)) in the laminate was changed to trimethoxy(2-phenylethyl)silane (β-PTS), resulting in a laminate containing doped Si, SiO2, β-PTS, and an organic semiconductor film. Otherwise, an organic semiconductor device was fabricated in the same manner as in Example 3.

[0326] exist Figure 24 The image shows a laser confocal microscopy photograph of the organic semiconductor (C9-DNBDT-NW) film observed on the upper surface of the fabricated organic semiconductor device. The entire surface enclosed by the dashed line (area: 450 mm²) is shown. 2 This method can yield monolayer single-crystal domain thin films.

[0327] exist Figure 25 The image shows measurements taken using atomic force microscopy (AFM). Figure 26 The results for the C9-DNBDT-NW monolayer film show that a thickness of 4 nm, equivalent to one molecular layer of C9-DNBDT-NW, can be obtained.

[0328] For a transistor with a channel length / channel width of 200μm / 1000μm, in Figure 27 The graph shown illustrates the transfer characteristics of the relationship between the gate voltage and drain current in the saturation region. Figure 28A graph showing transfer characteristics representing the relationship between the gate voltage and the drain current in the saturation region is shown in Fig. 6, and a graph showing transfer characteristics representing the relationship between the gate voltage and the drain current in the linear region is shown in Fig. 7. The mobility in the saturation region showed 15.3 cm Figure 29 A graph showing output characteristics representing the relationship between the drain voltage and the drain current based on the gate voltage is shown in Fig. 8. The mobility in the saturation region showed 2 cm 2 / V-s, and the mobility in the linear region showed 5.4 cm 2 / V-s, even if the organic semiconductor film is a single crystal of a monomolecular layer, a transistor with a very large mobility can be produced.

[0329] (Example 7)

[0330] A carrier injection promoting layer of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) was formed on the release layer by vacuum deposition, an Au electrode was formed on the carrier injection promoting layer in the same manner as in Example 3, and an organic semiconductor device was produced in the same manner as in Example 3, except for the above.

[0331] For the transistor produced with a channel length / channel width of 10 μm / 500 μm, a graph showing transfer characteristics representing the relationship between the gate voltage and the drain current in the saturation region is shown in Fig. 6, and a graph showing transfer characteristics representing the relationship between the gate voltage and the drain current in the linear region is shown in Fig. 7. The mobility in the saturation region showed 15.3 cm Figure 32 A graph showing output characteristics representing the relationship between the drain voltage and the drain current based on the gate voltage is shown in Fig. 8. The mobility in the saturation region showed 2 cm Figure 33 A graph showing output characteristics representing the relationship between the drain voltage and the drain current based on the gate voltage is shown in Fig. 8. The mobility in the saturation region showed 2 cm Figure 34 A graph showing output characteristics representing the relationship between the drain voltage and the drain current based on the gate voltage is shown in Fig. 8. The mobility in the saturation region showed 2 cm 2 / V-s, and the mobility in the linear region showed 5.4 cm 2 / V-s, a good mobility can be obtained.

[0332] (Example 8)

[0333] The release layer was changed to triethoxy-1H, 1H, 2H, 2H-heptadecafluorodecylsilane (F-SAM), the protective film was changed to CTX-809SP2 of CYTOP (registered trademark) with a terminal group of CF3 and a glass transition point of 108°C, and the diX-SR (registered trademark) in the laminate was changed to β-PTS, to obtain a laminate doped with Si, SiO2, β-PTS, and an organic semiconductor film, and an organic semiconductor device was produced in the same manner as in Example 3, except for the above.

[0334] The CTX-809SP2 protective film of CYTOP (registered trademark) was formed by the following method. A solution prepared so that CTX-809SP2: CT-Solv. 180 (dilution solvent) = 2:3 (mass ratio) was spin-coated on a glass substrate on which an Au electrode was formed under the same conditions as in Example 1. The rotation was stopped, and the solution was dried at 50°C for 1 minute and then at 80°C for 40 minutes to remove the solvent, thereby forming a 809SP2 protective film having a thickness of 300 nm. In order to be able to coat PVA, surface modification of the CTX-809SP2 was performed using excimer light, and a PVA-treated film was formed by the same method as in Example 1.

[0335] For the transistor having a channel length / channel width of 100 μm / 500 μm fabricated, a graph showing the transfer characteristics of the gate voltage versus the drain current in the saturation region is shown in FIG. 6, a graph showing the transfer characteristics of the gate voltage versus the drain current in the linear region is shown in FIG. 7, and a graph showing the output characteristics of the drain voltage versus the drain current based on the gate voltage is shown in FIG. 8. The mobility in the saturation region showed 12 cm Figure 35 / V-s, and the mobility in the linear region showed 13 cm Figure 36 / V-s, and the mobility in the linear region showed 13 cm Figure 37 / V-s, and the mobility in the linear region showed 13 cm 2 / V-s, and the mobility in the linear region showed 13 cm 2 / V-s, and the mobility in the linear region showed 13 cm

[0336] (Example 9)

[0337] Au electrodes each having a channel length / channel width of 100 μm / 500 μm, 80 μm / 500 μm, 60 μm / 500 μm, 40 μm / 500 μm, 20 μm / 500 μm, 10 μm / 500 μm, and 200 μm / 500 μm were formed in 16 groups, respectively, for a total of 112 groups, and the protective film was changed to CTL-809M of CYTOP (registered trademark) having a glass transition point of 108°C and having a terminal group of -CONH-Si(OR)n, and an organic semiconductor device was fabricated in the same manner as in Example 8, except for this.

[0338] The CTL-809M protective film was formed by the following method. A solution prepared so that CTL-809M: CT-Solv. 180 (dilution solvent) = 2:3 (mass ratio) was spin-coated on a glass substrate on which an Au electrode was formed under the same conditions as in Example 1. The rotation was stopped, and the solution was dried at 50°C for 40 minutes to remove the solvent, thereby forming a CTL-809M protective film having a thickness of 300 nm. In order to be able to coat PVA, surface modification of the CTL-809M protective film was performed using excimer light, and a PVA-treated film was formed by the same method as in Example 1.

[0339] For the transistor produced with a channel length / channel width of 200 μm / 500 μm, a graph showing transfer characteristics of the relationship between the gate voltage and the drain current in the saturation region is shown in FIG. 6, a graph showing transfer characteristics of the relationship between the gate voltage and the drain current in the linear region is shown in FIG. 7, and a graph showing output characteristics of the relationship between the drain voltage and the drain current based on the gate voltage is shown in FIG. 8. The mobility in the saturation region showed 15 cm Figure 38 / V-s, and the mobility in the linear region showed 11 cm Figure 39 / V-s, and the mobility in the linear region showed 11 cm Figure 40 / V-s, and the mobility in the linear region showed 11 cm 2 / V-s, and the mobility in the linear region showed 11 cm 2 / V-s, and the mobility in the linear region showed 11 cm

[0340] (Example 10)

[0341] The protective film was changed to polyadamantyl methacrylate (PADMA) having a glass transition point of 200°C or higher, and an organic semiconductor device was produced in the same manner as in Example 3, except for this.

[0342] The protective film of PADMA was formed by the following method. A solution in which 2 mass% of PADMA was dissolved in cyclohexane was spin-coated on a glass substrate on which an Au electrode was formed, under the same conditions as in Example 1. The rotation was stopped, and drying was performed at 50°C for 30 seconds, followed by drying at 80°C for 15 minutes, to remove the solvent, and a PADMA protective film having a thickness of 200 nm was formed.

[0343] For the transistor produced with a channel length / channel width of 80 μm / 500 μm, a graph showing transfer characteristics of the relationship between the gate voltage and the drain current in the saturation region is shown in FIG. 14, a graph showing transfer characteristics of the relationship between the gate voltage and the drain current in the linear region is shown in FIG. 15, and a graph showing output characteristics of the relationship between the drain voltage and the drain current based on the gate voltage is shown in FIG. 16. The mobility in the saturation region showed 4.7 cm Figure 43 / V-s, and the mobility in the linear region showed 7.0 cm Figure 44 / V-s, and the mobility in the linear region showed 7.0 cm Figure 45 / V-s, and the mobility in the linear region showed 7.0 cm 2 / V-s, and the mobility in the linear region showed 7.0 cm 2 / V-s, and the mobility in the linear region showed 7.0 cm

[0344] (Example 11)

[0345] Au electrodes each having a channel length / channel width of 100 μm / 500 μm, 80 μm / 500 μm, 60 μm / 500 μm, 40 μm / 500 μm, 20 μm / 500 μm, and 10 μm / 500 μm were formed in 8 groups, respectively, for a total of 48 groups, in the same manner as in Example 1, and an organic semiconductor device was produced in the same manner as in Example 6, except for this. Figure 45An organic semiconductor device of a cross-sectional structure shown schematically.

[0346] For the fabricated organic semiconductor device, the contact resistance was evaluated using a transmission line method (TLM) method. In Figure 46 the graph showing the relationship between each V G -V th , the channel length L and R total ·W, and in Figure 47 the graph showing the relationship between V G -V th and R C ·W. From Figure 48 it was confirmed that a low contact resistance of R C ·W of 175 Ω-cm or less was obtained.

[0347] (Example 12)

[0348] An EAGLE glass (EAGLE XG (registered trademark) of Corning Inc.) substrate was prepared as a substrate, and as shown schematically in Figure 49 a CYTOP (registered trademark) of CTL-809M having a thickness of 10 nm and a terminal group of -CONH-Si(OR)n was formed as a lyophobic polymer layer 80 on the surface of the substrate 60.

[0349] The CTL-809M lyophobic polymer layer was formed by the following method. A solution prepared by CTL-809M: CT-Solv. 180 (dilution solvent) = 1:30 (mass ratio) was spin-coated on a glass substrate. In the spin coating, the speed was increased to 500 rpm in 1 second, held at 500 rpm for 10 seconds, and held at 1000 rpm for 40 seconds. The rotation was stopped, and drying was performed at 50°C for 1 minute, then at 80°C for 15 minutes, and further at 130°C for 40 minutes to remove the solvent, and form a 809M lyophobic polymer layer having a thickness of 10 nm.

[0350] As shown schematically in Figure 52 a chromium photomask 82 was disposed on the glass substrate on which the lyophobic polymer layer 80 was formed, and vacuum ultraviolet light (VUV) 84 was irradiated from the side on which the photomask 82 was disposed. As shown schematically in Figure 53 the irradiated portion of the lyophobic polymer layer 80 was decomposed, and a hydroxyl group was formed at the portion after decomposition of the lyophobic polymer layer. The irradiation of the vacuum ultraviolet light was performed while moving a excimer lamp (wavelength 172 nm) at a speed of 0.04 mm / second under a N2 flow atmosphere using SUS1001 (manufactured by USHIO Electric Co., Ltd.).

[0351] AsFigure 50 As shown schematically, the surface of the glass substrate 60 having hydroxyl groups formed thereon is subjected to SAM treatment using a vapor phase method to form a fluorine-based self-assembled monolayer 86 of triethoxy-1H, 1H, 2H, 2H-heptadecafluorodecylsilane (F-SAM). The formation of the fluorine-based self-assembled monolayer is performed by placing a solution of F-SAM and the glass substrate having hydroxyl groups formed thereon in a closed container, heating to 120°C to form a saturated vapor atmosphere of F-SAM molecules, and leaving the glass substrate having hydroxyl groups formed thereon in the saturated vapor atmosphere of F-SAM molecules for 3 hours, followed by cleaning with 2-propanol.

[0352] Next, Ag ink (manufactured by ULVAC, Inc., L-Ag1T) having a solid content concentration of 30 wt% was diluted with octane to a solid content concentration of 50 times, and Ag ink containing Ag particles was prepared.

[0353] Here, evaluation results of the contact angle of octane as a solvent of Ag ink with respect to CYTOP (registered trademark) and F-SAM are shown. In Figure 51 A photograph showing evaluation of the contact angle of octane with respect to CYTOP (registered trademark) before irradiation of vacuum ultraviolet light is shown in Figure 54 A photograph showing evaluation of the contact angle of octane with respect to CYTOP (registered trademark) after vacuum ultraviolet light irradiation and SAM treatment, and F-SAM formed by vacuum ultraviolet light irradiation and SAM treatment is shown in

[0354] In either case before vacuum ultraviolet light irradiation and after SAM treatment, the contact angle of octane with respect to CYTOP (registered trademark) was 31°, and the contact angle of octane with respect to F-SAM was 21°. It was thus found that F-SAM was not formed on CYTOP (registered trademark) before and after SAM treatment, and F-SAM was selectively formed on the portion after irradiation of vacuum ultraviolet light. In addition, it was confirmed that CYTOP (registered trademark) was relatively hydrophobic with respect to octane, and F-SAM was relatively hydrophilic with respect to octane.

[0355] As Figure 55As shown schematically, the Ag ink, which is an octane-based solvent and in which the contact angle is confirmed as described above, is applied to the glass substrate 60 on which the self-assembled monolayer film 86 of the F-SAM is formed by a hanging plate coating method, to form a coating film composed of Ag particles 88 in a manner such that the distance between straight lines corresponding to the channel length is 10 μm and 20 μm. The coating film is not formed on the CYTOP (registered trademark) which is lyophobic, but is selectively formed only on the F-SAM which is lyophilic. In Figure 56 An appearance photograph of the resulting patterned coating film composed of Ag particles is shown in FIG. 12. The Ag ink containing Ag particles was prepared by diluting the solid content concentration of the Ag ink (manufactured by ULVAC, Inc., L-Ag1T) having a solid content concentration of 30 wt% with octane to 50 times.

[0356] (Example 13)

[0357] A coating film composed of Ag particles was formed in a manner such that the channel length / channel width was 100 μm / 1000 μm, and otherwise, the coating film composed of Ag particles was formed by the same method as in Example 12. As shown schematically in FIG. 11, the glass substrate 60 on which the coating film composed of Ag particles 88 was formed was subjected to non-electrolytic plating with the Ag particles 88 as a catalyst to form a patterned source / drain electrode having an Au plating layer 89. Figure 57

[0358] PRECIOUS FAB ACG3000 (Electroplating Engineers Of Japan, Inc.) was used as a plating solution for non-electrolytic plating. The pH of the plating solution was prepared to be 7.5 and the liquid temperature was maintained at 65°C, and the glass substrate on which the conductive ink was applied was immersed in the plating solution for 150 seconds while the plating solution was stirred. Subsequently, heating was performed using a hot plate at 150°C for 10 minutes, and after cooling to room temperature, it was again immersed for 150 seconds to grow Au.

[0359] An appearance photograph of the resulting source / drain electrode having an Au plating layer is shown in FIG. 14. The two sets of electrodes having the Au plating layer had a channel length / channel width = 100 μm / 1000 μm, and the surface roughness Rq was 0.5 nm. The surface roughness Rq was measured as described below, a protective film and a treatment film were formed, the Kapton tape was attached to the treatment film and stretched, and thus the surface roughness of the electrode surface after peeling off the self-assembled monolayer film was measured. Figure 58

[0360] (Example 14)

[0361] ​​A protective film of diX-SR (registered trademark) having a thickness of 1 μm was formed on the glass substrate on which the electrode having the Au plating layer made in Example 13 was formed by a chemical vapor deposition method.

[0362] A treatment film of PVA having a thickness of 10 μm was formed by applying a 5 mass% aqueous solution of polyvinyl alcohol (PVA) to the protective film of diX-SR (registered trademark) and drying at 50°C for 2 hours.

[0363] The electrode thin film including the electrode having the Au plating layer, the protective film of diX-SR (registered trademark) and the treatment film of PVA was peeled by adhering the treatment film of PVA to a Kapton tape and stretching the Kapton tape.

[0364] In the same manner as in Example 6, a laminate of the doped Si, SiO2, β-PTS and organic semiconductor film was prepared, and the electrode thin film was disposed on the organic semiconductor film with the electrode having the Au plating layer in contact with the organic semiconductor film.

[0365] The treatment film of PVA was dropped with water while being heated to 80°C, and after the treatment film was peeled off in essence, the temperature was lowered to 30°C and water was added until the entire electrode thin film was immersed in water. The treatment film was removed by stirring in water for 3 hours until the PVA was completely dissolved, and an organic field effect transistor of a bottom gate / top contact structure as schematically shown in the drawing was produced. Figure 58

[0366] (Example 15)

[0367] An electrode thin film including the electrode having the Au plating layer, the protective film of diX-SR (registered trademark) and the treatment film of PVA was obtained by the same method as in Example 14.

[0368] The work function of the electrode of the electrode thin film including the electrode having the Au plating layer, the protective film of diX-SR (registered trademark) and the treatment film of PVA as schematically shown in the drawing was measured by photoelectron yield spectroscopy (PYS). Figure 56 The measurement of the work function was performed using PYS-202 (Sumitomo Heavy Industries, Ltd.) by the following equation.

[0369] Y 1 / 2 ∝hv-W F

[0370] (In the equation, Y is the photoelectron yield, h is the Planck constant, v is the vibration number of the photon, and W is the work function). F

[0371] In Figure 59 ​​The diagram shows the Y phase plotted relative to the photon energy (hν). 1 / 2 The results of the work function determination. From Figure 60 The W of the electrode is obtained from the intersection of the two straight lines shown. F It is 5.2 eV. The W of gold F The W value of silver is 5.2 eV. F The work function of C9-DNBDT-NW is 4.3 eV, and the HOMO level is 5.24 eV. Therefore, it can be concluded that the work function of the gold deposited by electroless plating in the obtained electrode is dominant, which can yield a high work function that is beneficial for implanting organic semiconductor films into the substrate.

[0372] (Example 16)

[0373] Four groups of electrodes with Au plating layers were formed, each with a channel length / channel width of 40μm / 315μm, 60μm / 315μm, 80μm / 315μm, 100μm / 315μm, 120μm / 315μm, 140μm / 315μm, 160μm / 315μm, and 180μm / 315μm, for a total of 32 groups. In addition, an electrode film comprising an electrode with an Au plating layer, a Pyrelin (registered trademark) protective film, and a PVA treatment film was fabricated using the same method as in Example 12.

[0374] Similar to Example 6, a stack of Si, SiO2, β-PTS and an organic semiconductor film was prepared, and an electrode film with an Au-plated layer was disposed on the organic semiconductor film in such a way that the electrode film was connected to the organic semiconductor film.

[0375] Water is added dropwise to the PVA treatment membrane while it is heated to 80°C. After the treatment membrane is essentially peeled off, the temperature is lowered to 30°C and water is added until the entire electrode film is immersed in water. The mixture is stirred in the water for 3 hours until the PVA is completely dissolved, at which point the treatment membrane is removed, producing a product like... Figure 61 An organic field-effect transistor with a bottom-gate / top-contact structure is shown schematically.

[0376] Among the transistors fabricated with different channel lengths / channel widths, for Figure 62 The transistor shown has source and drain electrodes with a channel length / channel width of 100μm / 315μm. Figure 56 The graph shown illustrates the transfer characteristics of the relationship between the gate voltage and drain current in the saturation region. Figure 63 The graph shown illustrates the transfer characteristics of the relationship between the gate voltage and drain current in a linear region. Figure 64 The graph shows the output characteristics representing the relationship between drain voltage and drain current based on gate voltage. The mobility in the saturation region is shown to be 12.7 cm⁻¹. 2cm / Vs, the mobility of the linear region showed 11.8 cm 2 cm / Vs, showing a very large mobility. In the calculation of the mobility, the capacitance of the insulating film in which SiO2 and β-PTS were laminated was used as a theoretical value.

[0377] (Example 17)

[0378] The electrode having the Au plating layer having the channel length / channel width of 40 μm / 315 μm, 60 μm / 315 μm, 80 μm / 315 μm, 100 μm / 315 μm, 120 μm / 315 μm, 140 μm / 315 μm, 160 μm / 315 μm, and 180 μm / 315 μm fabricated in Example 16 was evaluated for the contact resistance. Figure 65 The bottom gate / top contact structure of the organic field effect transistor shown schematically was evaluated for the contact resistance. In Figure 66 the range in which the contact resistance was evaluated is indicated by a broken line.

[0379] The contact resistance was evaluated using a transmission line (TLM: Transmission Line Method) method. In Figure 66 the graph showing the relationship between V G -V th , the channel length L and R total • W is shown in Figure 1 the graph showing the relationship between V G -V th and R C • W. It was confirmed that R C • W was a low contact resistance of 120 Ω • cm.

[0380] (Example 18)

[0381] A plurality of the coating films composed of Ag particles having combined channel lengths / channel widths were formed in a range of 10 cm square, and otherwise, the Ag ink containing Ag particles was applied to the glass substrate on which the self-assembled monolayer film of the F-SAM was formed by a doctor blade coating method, and a patterned coating film composed of Ag particles was formed. In Figure 1 a photograph showing the appearance of the patterned coating film composed of Ag particles formed in a range of 10 cm square is shown. Figure 1The channel length / channel width of the coating film composed of Ag particles described in the above-mentioned patent publication includes: 784 sets of 100 μm / 800 μm; 170 sets each of 10 μm / 200 μm, 20 μm / 200 μm, 40 μm / 200 μm, 60 μm / 200 μm, 80 μm / 200 μm, 100 μm / 200 μm, 120 μm / 200 μm, 140 μm / 200 μm, 160 μm / 200 μm, 180 μm / 200 μm, and 200 μm / 200 μm; 34 sets each of 10 μm / 300 μm, 20 μm / 300 μm, 40 μm / 300 μm, 60 μm / 300 μm, 80 μm / 300 μm, 100 μm / 300 μm, 120 μm / 300 μm, 140 μm / 300 μm, 160 μm / 300 μm, 180 μm / 300 μm, and 200 μm / 300 μm; and 6 sets each of 100 μm / 6000 μm, 170 μm / 6000 μm, and 200 μm / 6000 μm.

[0382] The parallelism of the channel length of the coating film composed of Ag particles before plating of each set (one element) of electrodes was 0.1 degrees or less.

[0383] (Comparative Example 1)

[0384] A polydimethylsiloxane (PDMS) film having a thickness of 10 μm and having tackiness and a glass transition point of -123°C was prepared as an elastomer, and a Au plating layer electrode and a carrier injection promoting layer of F4-TCNQ were formed on the PDMS film with a metal mask interposed therebetween, to form one set of Au electrodes having a thickness of 40 nm and a channel length / channel width = 400 μm / 200 μm.

[0385] In the same manner as in Example 6, a laminate of a layer doped with Si, SiO2, β-PTS, and an organic semiconductor film was prepared, and Au electrodes, a carrier injection promoting layer of F4-TCNQ, and PDMS were disposed on the organic semiconductor film with the Au electrodes in contact with the organic semiconductor film, to produce an organic semiconductor device.

[0386] The change over time in the mobility of the linear region of the organic semiconductor devices produced in Example 6 and Comparative Example 1 is shown in Table 1. The transistor of the organic semiconductor device produced in Example 6 did not substantially change in mobility even after 4 weeks and after 8 weeks.

[0387] [Table 1]

[0388]

[0389] Explanation of Reference Numerals

[0390] 100: organic semiconductor device; 200: organic semiconductor device; 600: electrode thin film; 10: electrode; 101: face of electrode 10; 12: Figure 1 second group electrode of 10; 14: ​ third group electrode of 10; 20: electrode; 201: face of electrode 20; 22: ​ second group electrode of 20; 24: ​ third group electrode of 20; 30: protective film; 40: channel; 52: gate insulating film; 52-1: gate insulating film; 52-2: gate insulating film; 54: gate electrode; 56: base layer; 60: substrate; 62: release layer; 64: processing film; 66: organic semiconductor film; 70: base layer; 72: base layer; 74: gate electrode; 80: lyophobic polymer layer; 82: photomask or metal mask; 84: ultraviolet light; 86: self-assembled monolayer; 87: conductive ink; 88: metal particles; 89: plating layer.

Claims

1. A method for manufacturing an electrode for a source / drain of an organic semiconductor device, wherein the method for manufacturing an electrode for a source / drain of an organic semiconductor device comprises the steps of: preparing a substrate having a surface roughness Rq of 2 nm or less; forming a release layer on a surface of the substrate; forming 10 or more electrodes for a source / drain having a channel length of 200 μm or less on the release layer; forming a protective film on the release layer and the electrodes; forming a processing film on the protective film; releasing the interface of the release layer and the electrodes and the protective film to obtain an electrode film comprising the electrodes, the protective film, and the processing film; and removing the processing film.

2. A method for manufacturing an electrode for a source / drain of an organic semiconductor device, wherein the method for manufacturing an electrode for a source / drain of an organic semiconductor device comprises the steps of: preparing a substrate having a surface roughness Rq of 2 nm or less; forming a release layer on a surface of the substrate; forming 10 or more electrodes for a source / drain having a channel length of 200 μm or less on the release layer; forming a protective film on the release layer and the electrodes; forming a processing film on the protective film; releasing the interface of the release layer and the electrodes and the protective film to obtain an electrode film comprising the electrodes, the protective film, and the processing film; and removing the processing film.

3. A method for manufacturing an organic semiconductor device, wherein the method for manufacturing an organic semiconductor device comprises the steps of: preparing a substrate having a surface roughness Rq of 2 nm or less; forming a release layer on a surface of the substrate; forming 10 or more electrodes for a source / drain having a channel length of 200 μm or less on the release layer; forming a protective film on the release layer and the electrodes; forming a processing film on the protective film; releasing the interface of the release layer and the electrodes and the protective film to obtain an electrode film comprising the electrodes, the protective film, and the processing film; and removing the processing film. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ peeling the interface of the peeling layer from the electrode and the protective film to obtain an electrode thin film including the electrode, the protective film, and the processing film; arranging the electrode thin film on an organic semiconductor film; and removing the processing film, the step of forming the peeling layer includes the steps of: performing UV ozone treatment on the surface of the substrate to form hydroxyl groups on the surface of the substrate; and performing SAM treatment on the surface of the substrate on which the hydroxyl groups are formed.

4. A method for manufacturing an organic semiconductor device, wherein the method for manufacturing the organic semiconductor device includes the steps of: preparing a substrate having a surface roughness Rq of 2 nm or less; forming a peeling layer on the surface of the substrate; forming 10 or more groups of electrodes for source / drain having a channel length of 200 μm or less on the peeling layer; forming a protective film on the peeling layer and the electrodes; forming a processing film on the protective film; peeling the interface of the peeling layer from the electrode and the protective film to obtain an electrode thin film including the electrode, the protective film, and the processing film; arranging the electrode thin film on an organic semiconductor film; and removing the processing film, the step of forming the peeling layer includes the steps of: forming a lyophobic polymer layer on the surface of the substrate; arranging a photomask or a metal mask on the substrate on which the lyophobic polymer layer is formed; performing UV irradiation on the substrate from the side on which the photomask or the metal mask is arranged, decomposing the lyophobic polymer layer at the irradiated portion, and forming hydroxyl groups at the portion on which the lyophobic polymer layer is decomposed; and performing SAM treatment on the portion on which the hydroxyl groups are formed, the step of forming 10 or more groups of electrodes for source / drain having a channel length of 200 μm or less includes: applying a conductive ink including metal particles to the peeling layer; and performing non-electrolytic plating on the substrate on which the peeling layer to which the conductive ink is applied is formed, using the metal particles as a catalyst, to form 10 or more groups of electrodes for source / drain having the channel length of 200 μm or less and having plating layers. ​

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